Processes to control fouling and improve compositions

ABSTRACT

Improved reaction processes comprise reacting a mixture to form a product comprising a metal alkyl, metal oxide, or mixture thereof and then passing said product to a post-reactor heat exchanger. The improvement comprises one or more of the following: (1) reacting said metal alkyl compound with an acid to produce a soluble metal ester; or (2) adding an ionic surfactant; or (3) adding a mixture comprising an antioxidant to the product under conditions sufficient to avoid formation of significant amounts of insoluble metal or metal compounds derived from said metal alkyl compound; or (4) purging said post-reactor heat exchanger with an inert gas under conditions to remove metal oxide from the post-reactor heat exchanger.

FIELD OF THE INVENTION

This invention relates to improved processes employing a post-reactorheat exchanger. In particular, the invention relates to (1) reactionprocesses resulting in less heat exchanger fouling and (2) compositionswith improved characteristics, e.g., color.

BACKGROUND AND SUMMARY OF THE INVENTION

Many reaction processes employ heat exchangers in order to transfer heatfrom one media to another without the media being in direct contact. Theheat exchanger may be employed subsequent to the main reaction and insuch cases are called post-reactor heat exchangers. Unfortunately, insome situations these post-reactor heat exchangers may become fouled dueto impurities, for example, insoluble compounds building up in, forexample, coils or tubes of the heat exchanger. The fouling reduces thecross sectional area for heat to be transferred and causes an increasein the resistance to heat transfer across the heat exchanger. This isbecause the thermal conductivity of the fouling layer is often low.Thus, fouling reduces the overall heat transfer coefficient andefficiency of the heat exchanger. A corresponding increase in pumpingand maintenance cost may also result.

Accordingly, what is needed are improved processes which may assist inreducing or eliminating the fouling of equipment such as post-reactorheat exchangers.

Advantageously, improved reaction processes comprise reacting a mixturein a via a reaction in at least one reactor to form at least one productcomprising a metal alkyl compound, metal oxide, or mixture thereof andthen passing said product to a post-reactor heat exchanger. Theimprovement comprises one or more of the following:

(1) reacting said metal alkyl compound with an acid to produce a solublemetal ester; or

(2) adding an ionic surfactant to the reactor; or

(3) adding a mixture comprising an antioxidant to the product underconditions sufficient to avoid formation of significant amounts ofinsoluble metal or metal compounds derived from said metal alkylcompound; or

(4) purging said post-reactor heat exchanger with an inert gas underconditions to remove metal oxide from the post-reactor heat exchanger.

In another embodiment, the invention relates to novel compositionscomprising an ethylene/α-olefin multiblock interpolymer and a metalester. The ethylene/α-olefin multiblock interpolymers may becharacterized before any crosslinking by one or more of the followingcharacteristics:

(1) an average block index greater than zero and up to about 1.0 and amolecular weight distribution, Mw/Mn, greater than about 1.3; or

(2) at least one molecular fraction which elutes between 40° C. and 130°C. when fractionated using TREF, characterized in that the fraction hasa block index of at least 0.5 and up to about 1; or

(3) an Mw/Mn from about 1.7 to about 3.5, at least one melting point,Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter,wherein the numerical values of Tm and d correspond to the relationship:T _(m)>−6553.3+13735(d)−7051.7(d)²; or

(4) an Mw/Mn from about 1.7 to about 3.5, and a heat of fusion, ΔH inJ/g, and a delta quantity, ΔT, in degrees Celsius defined as thetemperature difference between the tallest DSC peak and the tallestCRYSTAF peak, wherein the numerical values of ΔT and ΔH have thefollowing relationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g,

wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or

(5) an elastic recovery, Re, in percent at 300 percent strain and 1cycle measured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenethylene/α-olefin interpolymer is substantially free of a cross-linkedphase:Re>1481−1629(d); or

(6) a molecular fraction which elutes between 40° C. and 130° C. whenfractionated using TREF, characterized in that the fraction has a molarcomonomer content of at least 5 percent higher than that of a comparablerandom ethylene interpolymer fraction eluting between the sametemperatures, wherein said comparable random ethylene interpolymer hasthe same comonomer(s) and has a melt index, density, and molar comonomercontent (based on the whole polymer) within 10 percent of that of theethylene/α-olefin interpolymer; or

(7) a storage modulus at 25° C., G′(25° C.), and a storage modulus at100° C., G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) isin the range of about 1:1 to about 9:1.

The ethylene/α-olefin multiblock interpolymer characteristics (1)through (7) above are given with respect to the ethylene/α-olefininterpolymer before any significant crosslinking, i.e., beforecrosslinking. The ethylene/α-olefin interpolymers useful in the presentinvention may or may not be crosslinked depending upon the desiredproperties. By using characteristics (1) through (7) as measured beforecrosslinking is not meant to suggest that the interpolymer is requiredor not required to be crosslinked—only that the characteristic ismeasured with respect to the interpolymer without significantcrosslinking. Crosslinking may or may not change each of theseproperties depending upon the specific polymer and degree ofcrosslinking.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the melting point/density relationship for the inventivepolymers (represented by diamonds) as compared to traditional randomcopolymers (represented by circles) and Ziegler-Natta copolymers(represented by triangles).

FIG. 2 shows plots of delta DSC—CRYSTAF as a function of DSC MeltEnthalpy for various polymers. The diamonds represent randomethylene/octene copolymers; the squares represent polymer examples 1-4;the triangles represent polymer examples 5-9; and the circles representpolymer examples 10-19. The “X” symbols represent polymer examplesA*-F*.

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms made from inventive interpolymers (represented by the squares andcircles) and traditional copolymers (represented by the triangles whichare various Dow AFFINITY® polymers). The squares represent inventiveethylene/butene copolymers; and the circles represent inventiveethylene/octene copolymers.

FIG. 4 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus TREF elution temperature ofthe fraction for the polymer of Example 5 (represented by the circles)and comparative polymers E and F (represented by the “X” symbols). Thediamonds represent traditional random ethylene/octene copolymers.

FIG. 5 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus TREF elution temperature ofthe fraction for the polymer of Example 5 (curve 1) and for comparativeF (curve 2). The squares represent Example F*; and the trianglesrepresent Example 5.

FIG. 6 is a graph of the log of storage modulus as a function oftemperature for comparative ethylene/1-octene copolymer (curve 2) andpropylene/ethylene-copolymer (curve 3) and for two ethylene/1-octeneblock copolymers of the invention made with differing quantities ofchain shuttling agent (curves 1).

FIG. 7 shows a plot of TMA (1 mm) versus flex modulus for some inventivepolymers (represented by the diamonds), as compared to some knownpolymers. The triangles represent various Dow VERSIFY® polymers; thecircles represent various random ethylene/styrene copolymers; and thesquares represent various Dow AFFINITY® polymers.

DETAILED DESCRIPTION OF THE INVENTION

General Definitions

“Polymer” means a polymeric compound prepared by polymerizing monomers,whether of the same or a different type. The generic term “polymer”embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as“interpolymer.”

“Interpolymer” means a polymer prepared by the polymerization of atleast two different types of monomers. The generic term “interpolymer”includes the term “copolymer” (which is usually employed to refer to apolymer prepared from two different monomers) as well as the term“terpolymer” (which is usually employed to refer to a polymer preparedfrom three different types of monomers). It also encompasses polymersmade by polymerizing four or more types of monomers.

The terms “ethylene/α-olefin block interpolymer” or “ethylene/α-olefinmultiblock interpolymer” generally refer to block copolymers comprisingethylene and an α-olefin having 3 or more carbon atoms. Preferably,ethylene comprises the majority mole fraction of the whole polymer,i.e., ethylene comprises at least about 50 mole percent of the wholepolymer. More preferably ethylene comprises at least about 60 molepercent, at least about 70 mole percent, or at least about 80 molepercent, with the substantial remainder of the whole polymer comprisingat least one other comonomer that is preferably an α-olefin having 3 ormore carbon atoms. For many ethylene/octene copolymers, the preferredcomposition comprises an ethylene content greater than about 80 molepercent of the whole polymer and an octene content of from about 10 toabout 15, preferably from about 15 to about 20 mole percent of the wholepolymer. In some embodiments, the ethylene/α-olefin block interpolymersdo not include those produced in low yields or in a minor amount or as aby-product of a chemical process. While the ethylene/α-olefin blockinterpolymers can be blended with one or more polymers, the as-producedethylene/α-olefin block interpolymers are substantially pure and oftencomprise a major component of the reaction product of a polymerizationprocess. Such ethylene/α-olefin block interpolymers are described in,for example, U.S. Patent Application Publication No. US 2006/0199930 A1published on Sep. 7, 2006 and incorporated herein by reference.

The terms “propylene-ethylene interpolymer” or “propylene basedplastomers or elastomers (PBPE)” generally refer to copolymerscomprising propylene and a monomer such as ethylene. Preferably,propylene comprises the majority mole fraction of the whole polymer,i.e., propylene comprises at least about 70, preferably at least about80, more preferably at least about 90 mole percent of the whole polymerwith a substantial remainder of the whole polymer comprising at leastone other comonomer that is preferably ethylene. Suitablepropylene-ethylene interpolymers are described in, for example, WO2006/115839 published on Nov. 2, 2006 and incorporated herein byreference. Suitable propylene-ethylene interpolymers are soldcommercially by The Dow Chemical Company as VERSIFY™ and by Exxon asVISTAMAXX™.

“Composition,” as used herein, includes a mixture of materials whichcomprise the composition, as well as reaction products and decompositionproducts formed from the ingredients or materials of the composition.Specifically included within the compositions of the present inventionare grafted or coupled compositions wherein an initiator or couplingagent reacts with at least a portion of one or more polymers and/or atleast a portion of one or more fillers.

Unless otherwise stated, for purposes of this application the testmethods used are described below or are well-known to one skilled in theart.

Density

Resin density was measured by the Archimedes displacement method, ASTM D792-03, Method B, in isopropanol. Specimens were measured within 1 hourof molding after conditioning in the isopropanol bath at 23° C. for 8min to achieve thermal equilibrium prior to measurement. The specimenswere compression molded according to ASTM D-4703-00 Annex A with a 5 mininitial heating period at about 190° C. and a 15° C./min cooling rateper Procedure C. The specimen was cooled to 45° C. in the press withcontinued cooling until “cool to the touch”.

Melt Flow Rate by Extrusion Plastomer

Melt flow rate measurements for polyethylene were performed according toASTM D-1238-03, Condition 190° C./2.16 kg and Condition 190° C./10.0 kg,which are known as I₂ and I₁₀, respectively. Melt flow rate measurementsfor PBPE and/or propylene polymers were performed according to ASTMD-1238-03, Condition 230° C./2.16 kg and Condition 230° C./10.0 kg,which are known as I₂ and I₁₀, respectively. Melt flow rate is inverselyproportional to the molecular weight of the polymer. Thus, the higherthe molecular weight, the lower the melt flow rate, although therelationship is not linear. Melt flow rate determinations can also beperformed with even higher weights, such as in accordance with ASTMD-1238 Condition 190° C./21.6 kg, and is known as I₂₁. Melt Flow RateRatio (MFRR) is the ratio of melt flow rate (I₁₀) to melt flow rate (I₂)unless otherwise specified.

DSC Glass Transition Temperature

Using a DSC TA Instruments model 2010, data was collected and reducedusing Universal Analysis software package. Circa 9-mg sample was weightusing a Mettler AE 240 analytical balance. Lightweight (ca 25 mg)aluminum pans were employed throughout. The pans were crimped to improvesample/pan contact. The below steps were employed:

Equilibrate at 40° C.

Ramp 10.00° C./min to 250.00° C.

Air cool: on

Ramp 20.00° C./min to 40.00° C.

Equilibrate at 40.00° C.

Air cool: Off

Ramp 10.00° C./min to 250.00° C.

Data storage: Off

Air cool: On

Ramp 20.00° C./min to 30.00° C.

Air cool: Off

The ethylene/α-olefin interpolymers comprise ethylene and one or morecopolymerizable α-olefin comonomers in polymerized form, characterizedby multiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties. That is, theethylene/α-olefin interpolymers are block interpolymers, preferablymulti-block interpolymers or copolymers. The terms “interpolymer” andcopolymer” are used interchangeably herein. In some embodiments, themulti-block copolymer can be represented by the following formula:(AB)_(n)

where n is at least 1, preferably an integer greater than 1, such as 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, “A”represents a hard block or segment and “B” represents a soft block orsegment. Preferably, As and Bs are linked in a substantially linearfashion, as opposed to a substantially branched or substantiallystar-shaped fashion. In other embodiments, A blocks and B blocks arerandomly distributed along the polymer chain. In other words, the blockcopolymers usually do not have a structure as follows.AAA-AA-BBB-BB

In still other embodiments, the block copolymers do not usually have athird type of block, which comprises different comonomer(s). In yetother embodiments, each of block A and block B has monomers orcomonomers substantially randomly distributed within the block. In otherwords, neither block A nor block B comprises two or more sub-segments(or sub-blocks) of distinct composition, such as a tip segment, whichhas a substantially different composition than the rest of the block.

The multi-block polymers typically comprise various amounts of “hard”and “soft” segments. “Hard” segments refer to blocks of polymerizedunits in which ethylene is present in an amount greater than about 95weight percent, and preferably greater than about 98 weight percentbased on the weight of the polymer. In other words, the comonomercontent (content of monomers other than ethylene) in the hard segmentsis less than about 5 weight percent, and preferably less than about 2weight percent based on the weight of the polymer. In some embodiments,the hard segments comprises all or substantially all ethylene. “Soft”segments, on the other hand, refer to blocks of polymerized units inwhich the comonomer content (content of monomers other than ethylene) isgreater than about 5 weight percent, preferably greater than about 8weight percent, greater than about 10 weight percent, or greater thanabout 15 weight percent based on the weight of the polymer. In someembodiments, the comonomer content in the soft segments can be greaterthan about 20 weight percent, greater than about 25 weight percent,greater than about 30 weight percent, greater than about 35 weightpercent, greater than about 40 weight percent, greater than about 45weight percent, greater than about 50 weight percent, or greater thanabout 60 weight percent.

The soft segments can often be present in a block interpolymer fromabout 1 weight percent to about 99 weight percent of the total weight ofthe block interpolymer, preferably from about 5 weight percent to about95 weight percent, from about 10 weight percent to about 90 weightpercent, from about 15 weight percent to about 85 weight percent, fromabout 20 weight percent to about 80 weight percent, from about 25 weightpercent to about 75 weight percent, from about 30 weight percent toabout 70 weight percent, from about 35 weight percent to about 65 weightpercent, from about 40 weight percent to about 60 weight percent, orfrom about 45 weight percent to about 55 weight percent of the totalweight of the block interpolymer. Conversely, the hard segments can bepresent in similar ranges. The soft segment weight percentage and thehard segment weight percentage can be calculated based on data obtainedfrom DSC or NMR. Such methods and calculations are disclosed in aconcurrently filed U.S. patent application Ser. No. 11/376,835, entitled“Ethylene/α-Olefin Block Interpolymers”, filed on Mar. 15, 2006, in thename of Colin L. P. Shan, Lonnie Hazlitt, et. al. and assigned to DowGlobal Technologies Inc., the disclosure of which is incorporated byreference herein in its entirety.

The term “crystalline” if employed, refers to a polymer that possesses afirst order transition or crystalline melting point (Tm) as determinedby differential scanning calorimetry (DSC) or equivalent technique. Theterm may be used interchangeably with the term “semicrystalline”. Theterm “amorphous” refers to a polymer lacking a crystalline melting pointas determined by differential scanning calorimetry (DSC) or equivalenttechnique.

The term “multi-block copolymer” or “segmented copolymer” refers to apolymer comprising two or more chemically distinct regions or segments(referred to as “blocks”) preferably joined in a linear manner, that is,a polymer comprising chemically differentiated units which are joinedend-to-end with respect to polymerized ethylenic functionality, ratherthan in pendent or grafted fashion. In a preferred embodiment, theblocks differ in the amount or type of comonomer incorporated therein,the density, the amount of crystallinity, the crystallite sizeattributable to a polymer of such composition, the type or degree oftacticity (isotactic or syndiotactic), regio-regularity orregio-irregularity, the amount of branching, including long chainbranching or hyper-branching, the homogeneity, or any other chemical orphysical property. The multi-block copolymers are characterized byunique distributions of both polydispersity index (PDI or Mw/Mn), blocklength distribution, and/or block number distribution due to the uniqueprocess making of the copolymers. More specifically, when produced in acontinuous process, the polymers desirably possess PDI from 1.7 to 2.9,preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and mostpreferably from 1.8 to 2.1. When produced in a batch or semi-batchprocess, the polymers possess PDI from 1.0 to 2.9, preferably from 1.3to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to1.8.

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or “approximate”is used in connection therewith. They may vary by 1 percent, 2 percent,5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical rangewith a lower limit, R^(L) and an upper limit, R^(U), is disclosed, anynumber falling within the range is specifically disclosed. Inparticular, the following numbers within the range are specificallydisclosed: R═R^(L)+k*(R^(U)−R^(L)), wherein k is a variable ranging from1 percent to 100 percent with a 1 percent increment, i.e., k is 1percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . , 50 percent,51 percent, 52 percent, . . . , 95 percent, 96 percent, 97 percent, 98percent, 99 percent, or 100 percent. Moreover, any numerical rangedefined by two R numbers as defined in the above is also specificallydisclosed.

(A) Ethylene/α-Olefin Interpolymers

The ethylene/α-olefin interpolymers used in embodiments of the invention(also referred to as “inventive interpolymer” or “inventive polymer”)comprise ethylene and one or more copolymerizable α-olefin comonomers inpolymerized form, characterized by multiple blocks or segments of two ormore polymerized monomer units differing in chemical or physicalproperties (block interpolymer), preferably a multi-block copolymer. Theethylene/α-olefin interpolymers are characterized by one or more of theaspects described as follows.

In one aspect, the ethylene/α-olefin interpolymers used in embodimentsof the invention have a M_(w)/M_(n) from about 1.7 to about 3.5 and atleast one melting point, T_(m), in degrees Celsius and density, d, ingrams/cubic centimeter, wherein the numerical values of the variablescorrespond to the relationship:T _(m)>−6553.3+13735(d)−7051.7(d)²; orT _(m)>−2002.9+4538.5(d)−2422.2(d)², and preferablyT _(m)≧−6288.1+13141(d)−6720.3(d)², and more preferablyT _(m)≧858.91−1825.3(d)+1112.8(d)².

Such melting point/density relationship is illustrated in FIG. 1. Unlikethe traditional random copolymers of ethylene/α-olefins whose meltingpoints decrease with decreasing densities, the inventive interpolymers(represented by diamonds) exhibit melting points substantiallyindependent of the density, particularly when density is between about0.87 g/cc to about 0.95 g/cc. For example, the melting point of suchpolymers are in the range of about 110° C. to about 130° C. when densityranges from 0.875 g/cc to about 0.945 g/cc. In some embodiments, themelting point of such polymers are in the range of about 115° C. toabout 125° C. when density ranges from 0.875 g/cc to about 0.945 g/cc.

In another aspect, the ethylene/α-olefin interpolymers comprise, inpolymerized form, ethylene and one or more α-olefins and arecharacterized by a ΔT, in degree Celsius, defined as the temperature forthe tallest Differential Scanning calorimetry (“DSC”) peak minus thetemperature for the tallest Crystallization Analysis Fractionation(“CRYSTAF”) peak and a heat of fusion in J/g, ΔH, and ΔT and ΔH satisfythe following relationships:ΔT>−0.1299(ΔH)+62.81, and preferablyΔT≧−0.1299(ΔH)+64.38, and more preferablyΔT≧−0.1299(ΔH)+65.95,for ΔH up to 130 J/g. Moreover, ΔT is equal to or greater than 48° C.for ΔH greater than 130 J/g. The CRYSTAF peak is determined using atleast 5 percent of the cumulative polymer (that is, the peak mustrepresent at least 5 percent of the cumulative polymer), and if lessthan 5 percent of the polymer has an identifiable CRYSTAF peak, then theCRYSTAF temperature is 30° C., and ΔH is the numerical value of the heatof fusion in J/g. More preferably, the highest CRYSTAF peak contains atleast 10 percent of the cumulative polymer. FIG. 2 shows plotted datafor inventive polymers as well as comparative examples. Integrated peakareas and peak temperatures are calculated by the computerized drawingprogram supplied by the instrument maker. The diagonal line shown forthe random ethylene octene comparative polymers corresponds to theequation ΔT=−0.1299 (ΔH)+62.81.

In yet another aspect, the ethylene/α-olefin interpolymers have amolecular fraction which elutes between 40° C. and 130° C. whenfractionated using Temperature Rising Elution Fractionation (“TREF”),characterized in that said fraction has a molar comonomer contenthigher, preferably at least 5 percent higher, more preferably at least10 percent higher, than that of a comparable random ethyleneinterpolymer fraction eluting between the same temperatures, wherein thecomparable random ethylene interpolymer contains the same comonomer(s),and has a melt index, density, and molar comonomer content (based on thewhole polymer) within 10 percent of that of the block interpolymer.Preferably, the Mw/Mn of the comparable interpolymer is also within 10percent of that of the block interpolymer and/or the comparableinterpolymer has a total comonomer content within 10 weight percent ofthat of the block interpolymer.

In still another aspect, the ethylene/α-olefin interpolymers arecharacterized by an elastic recovery, Re, in percent at 300 percentstrain and 1 cycle measured on a compression-molded film of anethylene/α-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of Re and d satisfy thefollowing relationship when ethylene/α-olefin interpolymer issubstantially free of a cross-linked phase:Re>1481−1629(d); and preferablyRe≧1491−1629(d); and more preferablyRe>1501−1629(d); and even more preferablyRe≧1511−1629(d).

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms made from certain inventive interpolymers and traditional randomcopolymers. For the same density, the inventive interpolymers havesubstantially higher elastic recoveries.

In some embodiments, the ethylene/α-olefin interpolymers have a tensilestrength above 10 MPa, preferably a tensile strength≧11 MPa, morepreferably a tensile strength≧13 MPa and/or an elongation at break of atleast 600 percent, more preferably at least 700 percent, highlypreferably at least 800 percent, and most highly preferably at least 900percent at a crosshead separation rate of 11 cm/minute.

In other embodiments, the ethylene/α-olefin interpolymers have (1) astorage modulus ratio, G′(25° C.)/G′(100° C.), of from 1 to 50,preferably from 1 to 20, more preferably from 1 to 10; and/or (2) a 70°C. compression set of less than 80 percent, preferably less than 70percent, especially less than 60 percent, less than 50 percent, or lessthan 40 percent, down to a compression set of 0 percent.

In still other embodiments, the ethylene/α-olefin interpolymers have a70° C. compression set of less than 80 percent, less than 70 percent,less than 60 percent, or less than 50 percent. Preferably, the 70° C.compression set of the interpolymers is less than 40 percent, less than30 percent, less than 20 percent, and may go down to about 0 percent.

In some embodiments, the ethylene/α-olefin interpolymers have a heat offusion of less than 85 J/g and/or a pellet blocking strength of equal toor less than 100 pounds/foot² (4800 Pa), preferably equal to or lessthan 50 lbs/ft² (2400 Pa), especially equal to or less than 5 lbs/ft²(240 Pa), and as low as 0 lbs/ft² (0 Pa).

In other embodiments, the ethylene/α-olefin interpolymers comprise, inpolymerized form, at least 50 mole percent ethylene and have a 70° C.compression set of less than 80 percent, preferably less than 70 percentor less than 60 percent, most preferably less than 40 to 50 percent anddown to close zero percent.

In some embodiments, the multi-block copolymers possess a PDI fitting aSchultz-Flory distribution rather than a Poisson distribution. Thecopolymers are further characterized as having both a polydisperse blockdistribution and a polydisperse distribution of block sizes andpossessing a most probable distribution of block lengths. Preferredmulti-block copolymers are those containing 4 or more blocks or segmentsincluding terminal blocks. More preferably, the copolymers include atleast 5, 10 or 20 blocks or segments including terminal blocks.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (“NMR”) spectroscopypreferred. Moreover, for polymers or blends of polymers havingrelatively broad TREF curves, the polymer desirably is firstfractionated using TREF into fractions each having an eluted temperaturerange of 10° C. or less. That is, each eluted fraction has a collectiontemperature window of 10° C. or less. Using this technique, said blockinterpolymers have at least one such fraction having a higher molarcomonomer content than a corresponding fraction of the comparableinterpolymer.

In another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks (i.e.,at least two blocks) or segments of two or more polymerized monomerunits differing in chemical or physical properties (blockedinterpolymer), most preferably a multi-block copolymer, said blockinterpolymer having a peak (but not just a molecular fraction) whichelutes between 40° C. and 130° C. (but without collecting and/orisolating individual fractions), characterized in that said peak, has acomonomer content estimated by infra-red spectroscopy when expandedusing a full width/half maximum (FWHM) area calculation, has an averagemolar comonomer content higher, preferably at least 5 percent higher,more preferably at least 10 percent higher, than that of a comparablerandom ethylene interpolymer peak at the same elution temperature andexpanded using a full width/half maximum (FWHM) area calculation,wherein said comparable random ethylene interpolymer has the samecomonomer(s) and has a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer. The full width/half maximum(FWHM) calculation is based on the ratio of methyl to methylene responsearea [CH₃/CH₂] from the ATREF infra-red detector, wherein the tallest(highest) peak is identified from the base line, and then the FWHM areais determined. For a distribution measured using an ATREF peak, the FWHMarea is defined as the area under the curve between T₁ and T₂, where T₁and T₂ are points determined, to the left and right of the ATREF peak,by dividing the peak height by two, and then drawing a line horizontalto the base line, that intersects the left and right portions of theATREF curve. A calibration curve for comonomer content is made usingrandom ethylene/α-olefin copolymers, plotting comonomer content from NMRversus FWHM area ratio of the TREF peak. For this infra-red method, thecalibration curve is generated for the same comonomer type of interest.The comonomer content of TREF peak of the inventive polymer can bedetermined by referencing this calibration curve using its FWHMmethyl:methylene area ratio [CH₃/CH₂] of the TREF peak.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (NMR) spectroscopypreferred. Using this technique, said blocked interpolymers has highermolar comonomer content than a corresponding comparable interpolymer.

Preferably, for interpolymers of ethylene and 1-octene, the blockinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity (−0.2013)T+20.07, more preferably greater than or equal to the quantity (−0.2013)T+21.07, where T is the numerical value of the peak elution temperatureof the TREF fraction being compared, measured in ° C.

FIG. 4 graphically depicts an embodiment of the block interpolymers ofethylene and 1-octene where a plot of the comonomer content versus TREFelution temperature for several comparable ethylene/1-octeneinterpolymers (random copolymers) are fit to a line representing(−0.2013) T+20.07 (solid line). The line for the equation (−0.2013)T+21.07 is depicted by a dotted line. Also depicted are the comonomercontents for fractions of several block ethylene/1-octene interpolymersof the invention (multi-block copolymers). All of the block interpolymerfractions have significantly higher 1-octene content than either line atequivalent elution temperatures. This result is characteristic of theinventive interpolymer and is believed to be due to the presence ofdifferentiated blocks within the polymer chains, having both crystallineand amorphous nature.

FIG. 5 graphically displays the TREF curve and comonomer contents ofpolymer fractions for Example 5 and comparative F discussed below. Thepeak eluting from 40 to 130° C., preferably from 60° C. to 95° C. forboth polymers is fractionated into three parts, each part eluting over atemperature range of less than 10° C. Actual data for Example 5 isrepresented by triangles. The skilled artisan can appreciate that anappropriate calibration curve may be constructed for interpolymerscontaining different comonomers and a line used as a comparison fittedto the TREF values obtained from comparative interpolymers of the samemonomers, preferably random copolymers made using a metallocene or otherhomogeneous catalyst composition. Inventive interpolymers arecharacterized by a molar comonomer content greater than the valuedetermined from the calibration curve at the same TREF elutiontemperature, preferably at least 5 percent greater, more preferably atleast 10 percent greater.

In addition to the above aspects and properties described herein, theinventive polymers can be characterized by one or more additionalcharacteristics. In one aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that said fractionhas a molar comonomer content higher, preferably at least 5 percenthigher, more preferably at least 10, 15, 20 or 25 percent higher, thanthat of a comparable random ethylene interpolymer fraction elutingbetween the same temperatures, wherein said comparable random ethyleneinterpolymer comprises the same comonomer(s), preferably it is the samecomonomer(s), and a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer.

Preferably, the above interpolymers are interpolymers of ethylene and atleast one α-olefin, especially those interpolymers having a wholepolymer density from about 0.855 to about 0.935 g/cm³, and moreespecially for polymers having more than about 1 mole percent comonomer,the blocked interpolymer has a comonomer content of the TREF fractioneluting between 40 and 130° C. greater than or equal to the quantity(−0.1356) T+13.89, more preferably greater than or equal to the quantity(−0.1356) T+14.93, and most preferably greater than or equal to thequantity (−0.2013)T+21.07, where T is the numerical value of the peakATREF elution temperature of the TREF fraction being compared, measuredin ° C.

Preferably, for the above interpolymers of ethylene and at least onealpha-olefin especially those interpolymers having a whole polymerdensity from about 0.855 to about 0.935 g/cm³, and more especially forpolymers having more than about 1 mole percent comonomer, the blockedinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity (−0.2013)T+20.07, more preferably greater than or equal to the quantity (−0.2013)T+21.07, where T is the numerical value of the peak elution temperatureof the TREF fraction being compared, measured in ° C.

In still another aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that every fractionhaving a comonomer content of at least about 6 mole percent, has amelting point greater than about 100° C. For those fractions having acomonomer content from about 3 mole percent to about 6 mole percent,every fraction has a DSC melting point of about 110° C. or higher. Morepreferably, said polymer fractions, having at least 1 mole percentcomonomer, has a DSC melting point that corresponds to the equation:Tm≧(−5.5926)(mole percent comonomer in the fraction)+135.90.

In yet another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties (blocked interpolymer), most preferably amulti-block copolymer, said block interpolymer having a molecularfraction which elutes between 40° C. and 130° C., when fractionatedusing TREF increments, characterized in that every fraction that has anATREF elution temperature greater than or equal to about 76° C., has amelt enthalpy (heat of fusion) as measured by DSC, corresponding to theequation:Heat of fusion(J/gm)≦(3.1718)(ATREF elution temperature inCelsius)−136.58,

The inventive block interpolymers have a molecular fraction which elutesbetween 40° C. and 130° C., when fractionated using TREF increments,characterized in that every fraction that has an ATREF elutiontemperature between 40° C. and less than about 76° C., has a meltenthalpy (heat of fusion) as measured by DSC, corresponding to theequation:Heat of fusion(J/gm)≦(1.1312)(ATREF elution temperature inCelsius)+22.97.ATREF Peak Comonomer Composition Measurement by Infra-Red Detector

The comonomer composition of the TREF peak can be measured using an IR4infra-red detector available from Polymer Char, Valencia, Spain(http://www.polymerchar.com/).

The “composition mode” of the detector is equipped with a measurementsensor (CH₂) and composition sensor (CH₃) that are fixed narrow bandinfra-red filters in the region of 2800-3000 cm⁻¹. The measurementsensor detects the methylene (CH₂) carbons on the polymer (whichdirectly relates to the polymer concentration in solution) while thecomposition sensor detects the methyl (CH₃) groups of the polymer. Themathematical ratio of the composition signal (CH₃) divided by themeasurement signal (CH₂) is sensitive to the comonomer content of themeasured polymer in solution and its response is calibrated with knownethylene alpha-olefin copolymer standards.

The detector when used with an ATREF instrument provides both aconcentration (CH₂) and composition (CH₃) signal response of the elutedpolymer during the TREF process. A polymer specific calibration can becreated by measuring the area ratio of the CH₃ to CH₂ for polymers withknown comonomer content (preferably measured by NMR). The comonomercontent of an ATREF peak of a polymer can be estimated by applying a thereference calibration of the ratio of the areas for the individual CH₃and CH₂ response (i.e. area ratio CH₃/CH₂ versus comonomer content).

The area of the peaks can be calculated using a full width/half maximum(FWHM) calculation after applying the appropriate baselines to integratethe individual signal responses from the TREF chromatogram. The fullwidth/half maximum calculation is based on the ratio of methyl tomethylene response area [CH₃/CH₂] from the ATREF infra-red detector,wherein the tallest (highest) peak is identified from the base line, andthen the FWHM area is determined. For a distribution measured using anATREF peak, the FWHM area is defined as the area under the curve betweenT1 and T2, where T1 and T2 are points determined, to the left and rightof the ATREF peak, by dividing the peak height by two, and then drawinga line horizontal to the base line, that intersects the left and rightportions of the ATREF curve.

The application of infra-red spectroscopy to measure the comonomercontent of polymers in this ATREF-infra-red method is, in principle,similar to that of GPC/FTIR systems as described in the followingreferences: Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley;“Development of gel-permeation chromatography-Fourier transform infraredspectroscopy for characterization of ethylene-based polyolefincopolymers”. Polymeric Materials Science and Engineering (1991), 65,98-100.; and Deslauriers, P. J.; Rohlfing, D. C.; Shieh, E. T.;“Quantifying short chain branching microstructures in ethylene-1-olefincopolymers using size exclusion chromatography and Fourier transforminfrared spectroscopy (SEC-FTIR)”, Polymer (2002), 43, 59-170, both ofwhich are incorporated by reference herein in their entirety.

In other embodiments, the inventive ethylene/α-olefin interpolymer ischaracterized by an average block index, ABI, which is greater than zeroand up to about 1.0 and a molecular weight distribution, M_(w)/M_(n),greater than about 1.3. The average block index, ABI, is the weightaverage of the block index (“BI”) for each of the polymer fractionsobtained in preparative TREF from 20° C. and 110° C., with an incrementof 5° C.:ABI=Σ(w _(i) BI _(i))where BI_(i) is the block index for the ith fraction of the inventiveethylene/α-olefin interpolymer obtained in preparative TREF, and w_(i)is the weight percentage of the ith fraction.

For each polymer fraction, BI is defined by one of the two followingequations (both of which give the same BI value):

${BI} = \frac{{1/T_{X}} - {1/T_{XO}}}{{1/T_{A}} - {1/T_{AB}}}$ or${BI} = {- \frac{{{Ln}\; P_{X}} - {{Ln}\; P_{XO}}}{{{Ln}\; P_{A}} - {{Ln}\; P_{AB}}}}$where T_(X) is the preparative ATREF elution temperature for the ithfraction (preferably expressed in Kelvin), P_(X) is the ethylene molefraction for the ith fraction, which can be measured by NMR or IR asdescribed above. P_(AB) is the ethylene mole fraction of the wholeethylene/α-olefin interpolymer (before fractionation), which also can bemeasured by NMR or IR. T_(A) and P_(A) are the ATREF elution temperatureand the ethylene mole fraction for pure “hard segments” (which refer tothe crystalline segments of the interpolymer). As a first orderapproximation, the T_(A) and P_(A) values are set to those for highdensity polyethylene homopolymer, if the actual values for the “hardsegments” are not available. For calculations performed herein, T_(A) is372° K, P_(A) is 1.

T_(AB) is the ATREF temperature for a random copolymer of the samecomposition and having an ethylene mole fraction of P_(AB). T_(AB) canbe calculated from the following equation:Ln P _(AB) =α/T _(AB)+βwhere α and β are two constants which can be determined by calibrationusing a number of known random ethylene copolymers. It should be notedthat α and β may vary from instrument to instrument. Moreover, one wouldneed to create their own calibration curve with the polymer compositionof interest and also in a similar molecular weight range as thefractions. There is a slight molecular weight effect. If the calibrationcurve is obtained from similar molecular weight ranges, such effectwould be essentially negligible. In some embodiments, random ethylenecopolymers satisfy the following relationship:Ln P=−237.83/T _(ATREF)+0.639T_(XO) is the ATREF temperature for a random copolymer of the samecomposition and having an ethylene mole fraction of P_(X). T_(XO) can becalculated from LnP_(X)=α/T_(XO)+β. Conversely, P_(XO) is the ethylenemole fraction for a random copolymer of the same composition and havingan ATREF temperature of T_(X), which can be calculated from LnP_(XO)=α/T_(X)+β.

Once the block index (BI) for each preparative TREF fraction isobtained, the weight average block index, ABI, for the whole polymer canbe calculated. In some embodiments, ABI is greater than zero but lessthan about 0.3 or from about 0.1 to about 0.3. In other embodiments, ABIis greater than about 0.3 and up to about 1.0. Preferably, ABI should bein the range of from about 0.4 to about 0.7, from about 0.5 to about0.7, or from about 0.6 to about 0.9. In some embodiments, ABE is in therange of from about 0.3 to about 0.9, from about 0.3 to about 0.8, orfrom about 0.3 to about 0.7, from about 0.3 to about 0.6, from about 0.3to about 0.5, or from about 0.3 to about 0.4. In other embodiments, ABIis in the range of from about 0.4 to about 1.0, from about 0.5 to about1.0, or from about 0.6 to about 1.0, from about 0.7 to about 1.0, fromabout 0.8 to about 1.0, or from about 0.9 to about 1.0.

Another characteristic of the inventive ethylene/α-olefin interpolymeris that the inventive ethylene/α-olefin interpolymer comprises at leastone polymer fraction which can be obtained by preparative TREF, whereinthe fraction has a block index greater than about 0.1 and up to about1.0 and a molecular weight distribution, M_(w)/M_(n), greater than about1.3. In some embodiments, the polymer fraction has a block index greaterthan about 0.6 and up to about 1.0, greater than about 0.7 and up toabout 1.0, greater than about 0.8 and up to about 1.0, or greater thanabout 0.9 and up to about 1.0. In other embodiments, the polymerfraction has a block index greater than about 0.1 and up to about 1.0,greater than about 0.2 and up to about 1.0, greater than about 0.3 andup to about 1.0, greater than about 0.4 and up to about 1.0, or greaterthan about 0.4 and up to about 1.0. In still other embodiments, thepolymer fraction has a block index greater than about 0.1 and up toabout 0.5, greater than about 0.2 and up to about 0.5, greater thanabout 0.3 and up to about 0.5, or greater than about 0.4 and up to about0.5. In yet other embodiments, the polymer fraction has a block indexgreater than about 0.2 and up to about 0.9, greater than about 0.3 andup to about 0.8, greater than about 0.4 and up to about 0.7, or greaterthan about 0.5 and up to about 0.6.

For copolymers of ethylene and an α-olefin, the inventive polymerspreferably possess (1) a PDI of at least 1.3, more preferably at least1.5, at least 1.7, or at least 2.0, and most preferably at least 2.6, upto a maximum value of 5.0, more preferably up to a maximum of 3.5, andespecially up to a maximum of 2.7; (2) a heat of fusion of 80 J/g orless; (3) an ethylene content of at least 50 weight percent; (4) a glasstransition temperature, T_(g), of less than −25° C., more preferablyless than −30° C., and/or (5) one and only one T_(m).

Further, the inventive polymers can have, alone or in combination withany other properties disclosed herein, a storage modulus, G′, such thatlog(G′) is greater than or equal to 400 kPa, preferably greater than orequal to 1.0 MPa, at a temperature of 100° C. Moreover, the inventivepolymers possess a relatively flat storage modulus as a function oftemperature in the range from 0 to 100° C. (illustrated in FIG. 6) thatis characteristic of block copolymers, and heretofore unknown for anolefin copolymer, especially a copolymer of ethylene and one or moreC₃₋₈ aliphatic α-olefins. (By the term “relatively flat” in this contextis meant that log G′ (in Pascals) decreases by less than one order ofmagnitude between 50 and 100° C., preferably between 0 and 100° C.).

The inventive interpolymers may be further characterized by athermomechanical analysis penetration depth of 1 mm at a temperature ofat least 90° C. as well as a flexural modulus of from 3 kpsi (20 MPa) to13 kpsi (90 MPa). Alternatively, the inventive interpolymers can have athermomechanical analysis penetration depth of 1 mm at a temperature ofat least 104° C. as well as a flexural modulus of at least 3 kpsi (20MPa). They may be characterized as having an abrasion resistance (orvolume loss) of less than 90 mm³. FIG. 7 shows the TMA (1 mm) versusflex modulus for the inventive polymers, as compared to other knownpolymers. The inventive polymers have significantly betterflexibility-heat resistance balance than the other polymers.

Additionally, the ethylene/α-olefin interpolymers can have a melt index,I₂, from 0.01 to 2000 g/10 minutes, preferably from 0.01 to 1000 g/10minutes, more preferably from 0.01 to 500 g/10 minutes, and especiallyfrom 0.01 to 100 g/10 minutes. In certain embodiments, theethylene/α-olefin interpolymers have a melt index, 12, from 0.01 to 10g/10 minutes, from 0.5 to 50 g/10 minutes, from 1 to 30 g/10 minutes,from 1 to 6 g/10 minutes or from 0.3 to 10 g/10 minutes. In certainembodiments, the melt index for the ethylene/α-olefin polymers is 1 g/10minutes, 3 g/10 minutes or 5 g/10 minutes.

The polymers can have molecular weights, M_(w), from 1,000 g/mole to5,000,000 g/mole, preferably from 1000 g/mole to 1,000,000, morepreferably from 10,000 g/mole to 500,000 g/mole, and especially from10,000 g/mole to 300,000 g/mole. The density of the inventive polymerscan be from 0.80 to 0.99 g/cm³ and preferably for ethylene containingpolymers from 0.85 g/cm³ to 0.97 g/cm³. In certain embodiments, thedensity of the ethylene/α-olefin polymers ranges from 0.860 to 0.925g/cm³ or 0.867 to 0.910 g/cm³.

The process of making the polymers has been disclosed in the followingpatent applications: U.S. Provisional Application No. 60/553,906, filedMar. 17, 2004; U.S. Provisional Application No. 60/662,937, filed Mar.17, 2005; U.S. Provisional Application No. 60/662,939, filed Mar. 17,2005; U.S. Provisional Application No. 60/566,2938, filed Mar. 17, 2005;PCT Application No. PCT/US2005/008916, filed Mar. 17, 2005; PCTApplication No. PCT/US2005/008915, filed Mar. 17, 2005; and PCTApplication No. PCT/US2005/008917, filed Mar. 17, 2005, all of which areincorporated by reference herein in their entirety. For example, onesuch method comprises contacting ethylene and optionally one or moreaddition polymerizable monomers other than ethylene under additionpolymerization conditions with a catalyst composition comprising:

the admixture or reaction product resulting from combining:

(A) a first olefin polymerization catalyst having a high comonomerincorporation index,

(B) a second olefin polymerization catalyst having a comonomerincorporation index less than 90 percent, preferably less than 50percent, most preferably less than 5 percent of the comonomerincorporation index of catalyst (A), and

(C) a chain shuttling agent.

Representative catalysts and chain shuttling agent are as follows.

Catalyst (A1) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740.

Catalyst (A2) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-methylphenyl)(1,2-phenylene-(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740.

Catalyst (A3) isbis[N,N′″-(2,4,6-tri(methylphenyl)amido)ethylenediamine]hafniumdibenzyl.

Catalyst (A4) isbis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)cyclohexane-1,2-diylzirconium (IV) dibenzyl, prepared substantially according to theteachings of US-A-2004/0010103.

Catalyst (B1) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconium dibenzyl

Catalyst (B2) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(2-methylcyclohexyl)-immino)methyl)(2-oxoyl)zirconium dibenzyl

Catalyst (C1) is(t-butylamido)dimethyl(3-N-pyrrolyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the techniques of U.S. Pat.No. 6,268,444:

Catalyst (C2) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings ofUS-A-2003/004286:

Catalyst (C3) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,8a-η-s-indacen-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings ofUS-A-2003/004286:

Catalyst (D1) is bis(dimethyldisiloxane)(indene-1-yl)zirconiumdichloride available from Sigma-Aldrich:

Shuttling Agents The shuttling agents employed include diethylzinc,di(i-butyl)zinc, di(n-hexyl)zinc, triethylaluminum, trioctylaluminum,triethylgallium, i-butylaluminum bis(dimethyl(t-butyl)siloxane),i-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminumdi(pyridine-2-methoxide), bis(n-octadecyl)i-butylaluminum,i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminumbis(2,6-di-t-butylphenoxide, n-octylaluminum di(ethyl(1-naphthyl)amide),ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminumdi(bis(trimethylsilyl)amide), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), andethylzinc (t-butoxide).

Preferably, the foregoing process takes the form of a continuoussolution process for forming block copolymers, especially multi-blockcopolymers, preferably linear multi-block copolymers of two or moremonomers, more especially ethylene and a C₃₋₂₀ olefin or cycloolefin,and most especially ethylene and a C₄₋₂₀ α-olefin, using multiplecatalysts that are incapable of interconversion. That is, the catalystsare chemically distinct. Under continuous solution polymerizationconditions, the process is ideally suited for polymerization of mixturesof monomers at high monomer conversions. Under these polymerizationconditions, shuttling from the chain shuttling agent to the catalystbecomes advantaged compared to chain growth, and multi-block copolymers,especially linear multi-block copolymers are formed in high efficiency.

The inventive interpolymers may be differentiated from conventional,random copolymers, physical blends of polymers, and block copolymersprepared via sequential monomer addition, fluxional catalysts, anionicor cationic living polymerization techniques. In particular, compared toa random copolymer of the same monomers and monomer content atequivalent crystallinity or modulus, the inventive interpolymers havebetter (higher) heat resistance as measured by melting point, higher TMApenetration temperature, higher high-temperature tensile strength,and/or higher high-temperature torsion storage modulus as determined bydynamic mechanical analysis. Compared to a random copolymer containingthe same monomers and monomer content, the inventive interpolymers havelower compression set, particularly at elevated temperatures, lowerstress relaxation, higher creep resistance, higher tear strength, higherblocking resistance, faster setup due to higher crystallization(solidification) temperature, higher recovery (particularly at elevatedtemperatures), better abrasion resistance, higher retractive force, andbetter oil and filler acceptance.

The inventive interpolymers also exhibit a unique crystallization andbranching distribution relationship. That is, the inventiveinterpolymers have a relatively large difference between the tallestpeak temperature measured using CRYSTAF and DSC as a function of heat offusion, especially as compared to random copolymers containing the samemonomers and monomer level or physical blends of polymers, such as ablend of a high density polymer and a lower density copolymer, atequivalent overall density. It is believed that this unique feature ofthe inventive interpolymers is due to the unique distribution of thecomonomer in blocks within the polymer backbone. In particular, theinventive interpolymers may comprise alternating blocks of differingcomonomer content (including homopolymer blocks). The inventiveinterpolymers may also comprise a distribution in number and/or blocksize of polymer blocks of differing density or comonomer content, whichis a Schultz-Flory type of distribution. In addition, the inventiveinterpolymers also have a unique peak melting point and crystallizationtemperature profile that is substantially independent of polymerdensity, modulus, and morphology. In a preferred embodiment, themicrocrystalline order of the polymers demonstrates characteristicspherulites and lamellae that are distinguishable from random or blockcopolymers, even at PDI values that are less than 1.7, or even less than1.5, down to less than 1.3.

Moreover, the inventive interpolymers may be prepared using techniquesto influence the degree or level of blockiness. That is the amount ofcomonomer and length of each polymer block or segment can be altered bycontrolling the ratio and type of catalysts and shuttling agent as wellas the temperature of the polymerization, and other polymerizationvariables. A surprising benefit of this phenomenon is the discovery thatas the degree of blockiness is increased, the optical properties, tearstrength, and high temperature recovery properties of the resultingpolymer are improved. In particular, haze decreases while clarity, tearstrength, and high temperature recovery properties increase as theaverage number of blocks in the polymer increases. By selectingshuttling agents and catalyst combinations having the desired chaintransferring ability (high rates of shuttling with low levels of chaintermination) other forms of polymer termination are effectivelysuppressed. Accordingly, little if any β-hydride elimination is observedin the polymerization of ethylene/α-olefin comonomer mixtures accordingto embodiments of the invention, and the resulting crystalline blocksare highly, or substantially completely, linear, possessing little or nolong chain branching.

Polymers with highly crystalline chain ends can be selectively preparedin accordance with embodiments of the invention. In elastomerapplications, reducing the relative quantity of polymer that terminateswith an amorphous block reduces the intermolecular dilutive effect oncrystalline regions. This result can be obtained by choosing chainshuttling agents and catalysts having an appropriate response tohydrogen or other chain terminating agents. Specifically, if thecatalyst which produces highly crystalline polymer is more susceptibleto chain termination (such as by use of hydrogen) than the catalystresponsible for producing the less crystalline polymer segment (such asthrough higher comonomer incorporation, regio-error, or atactic polymerformation), then the highly crystalline polymer segments willpreferentially populate the terminal portions of the polymer. Not onlyare the resulting terminated groups crystalline, but upon termination,the highly crystalline polymer forming catalyst site is once againavailable for reinitiation of polymer formation. The initially formedpolymer is therefore another highly crystalline polymer segment.Accordingly, both ends of the resulting multi-block copolymer arepreferentially highly crystalline.

The ethylene α-olefin interpolymers used in the embodiments of theinvention are preferably interpolymers of ethylene with at least oneC₃-C₂₀ α-olefin. Copolymers of ethylene and a C₃-C₂₀ α-olefin areespecially preferred. The interpolymers may further comprise C₄-C₁₈diolefin and/or alkenylbenzene. Suitable unsaturated comonomers usefulfor polymerizing with ethylene include, for example, ethylenicallyunsaturated monomers, conjugated or nonconjugated dienes, polyenes,alkenylbenzenes, etc. Examples of such comonomers include C₃-C₂₀α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and thelike. 1-Butene and 1-octene are especially preferred. Other suitablemonomers include styrene, halo- or alkyl-substituted styrenes,vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics(e.g., cyclopentene, cyclohexene and cyclooctene).

While ethylene/α-olefin interpolymers are preferred polymers, otherethylene/olefin polymers may also be used. Olefins as used herein referto a family of unsaturated hydrocarbon-based compounds with at least onecarbon-carbon double bond. Depending on the selection of catalysts, anyolefin may be used in embodiments of the invention. Preferably, suitableolefins are C₃-C₂₀ aliphatic and aromatic compounds containing vinylicunsaturation, as well as cyclic compounds, such as cyclobutene,cyclopentene, dicyclopentadiene, and norbornene, including but notlimited to, norbornene substituted in the 5 and 6 position with C₁-C₂₀hydrocarbyl or cyclohydrocarbyl groups. Also included are mixtures ofsuch olefins as well as mixtures of such olefins with C₄-C₄₀ diolefincompounds.

Examples of olefin monomers include, but are not limited to propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene,4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene,vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene,cyclohexene, dicyclopentadiene, cyclooctene, C₄-C₄₀ dienes, includingbut not limited to 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene,1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C₄-C₄₀ α-olefins, andthe like. In certain embodiments, the α-olefin is propylene, 1-butene,1-pentene, 1-hexene, 1-octene or a combination thereof. Although anyhydrocarbon containing a vinyl group potentially may be used inembodiments of the invention, practical issues such as monomeravailability, cost, and the ability to conveniently remove unreactedmonomer from the resulting polymer may become more problematic as themolecular weight of the monomer becomes too high.

The polymerization processes described herein are well suited for theproduction of olefin polymers comprising monovinylidene aromaticmonomers including styrene, o-methyl styrene, p-methyl styrene,t-butylstyrene, and the like. In particular, interpolymers comprisingethylene and styrene can be prepared by following the teachings herein.Optionally, copolymers comprising ethylene, styrene and a C₃-C₂₀ alphaolefin, optionally comprising a C₄-C₂₀ diene, having improved propertiescan be prepared.

Suitable non-conjugated diene monomers can be a straight chain, branchedchain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms.Examples of suitable non-conjugated dienes include, but are not limitedto, straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene,1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene;3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene anddihydroocinene, single ring alicyclic dienes, such as1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ringdienes, such as tetrahydroindene, methyl tetrahydroindene,dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene,cycloalkenyl and cycloalkylidene norbornenes, such as5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene,5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene,5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene.Of the dienes typically used to prepare EPDMs, the particularlypreferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene(ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB),and dicyclopentadiene (DCPD). The especially preferred dienes are5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

One class of desirable polymers that can be made in accordance withembodiments of the invention are elastomeric interpolymers of ethylene,a C₃-C₂₀ α-olefin, especially propylene, and optionally one or morediene monomers. Preferred α-olefins for use in this embodiment of thepresent invention are designated by the formula CH₂═CHR*, where R* is alinear or branched alkyl group of from 1 to 12 carbon atoms. Examples ofsuitable α-olefins include, but are not limited to, propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and1-octene. A particularly preferred α-olefin is propylene. The propylenebased polymers are generally referred to in the art as EP or EPDMpolymers. Suitable dienes for use in preparing such polymers, especiallymulti-block EPDM type polymers include conjugated or non-conjugated,straight or branched chain-, cyclic- or polycyclic-dienes comprisingfrom 4 to 20 carbons. Preferred dienes include 1,4-pentadiene,1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene,cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferreddiene is 5-ethylidene-2-norbornene.

Because the diene containing polymers comprise alternating segments orblocks containing greater or lesser quantities of the diene (includingnone) and α-olefin (including none), the total quantity of diene andα-olefin may be reduced without loss of subsequent polymer properties.That is, because the diene and α-olefin monomers are preferentiallyincorporated into one type of block of the polymer rather than uniformlyor randomly throughout the polymer, they are more efficiently utilizedand subsequently the crosslink density of the polymer can be bettercontrolled. Such crosslinkable elastomers and the cured products haveadvantaged properties, including higher tensile strength and betterelastic recovery.

In some embodiments, the inventive interpolymers made with two catalystsincorporating differing quantities of comonomer have a weight ratio ofblocks formed thereby from 95:5 to 5:95. The elastomeric polymersdesirably have an ethylene content of from 20 to 90 percent, a dienecontent of from 0.1 to 10 percent, and an α-olefin content of from 10 to80 percent, based on the total weight of the polymer. Furtherpreferably, the multi-block elastomeric polymers have an ethylenecontent of from 60 to 90 percent, a diene content of from 0.1 to 10percent, and an α-olefin content of from 10 to 40 percent, based on thetotal weight of the polymer. Preferred polymers are high molecularweight polymers, having a weight average molecular weight (Mw) from10,000 to about 2,500,000, preferably from 20,000 to 500,000, morepreferably from 20,000 to 350,000, and a polydispersity less than 3.5,more preferably less than 3.0, and a Mooney viscosity (ML (1+4) 125° C.)from 1 to 250. More preferably, such polymers have an ethylene contentfrom 65 to 75 percent, a diene content from 0 to 6 percent, and anα-olefin content from 20 to 35 percent.

The ethylene/α-olefin interpolymers can be functionalized byincorporating at least one functional group in its polymer structure.Exemplary functional groups may include, for example, ethylenicallyunsaturated mono- and di-functional carboxylic acids, ethylenicallyunsaturated mono- and di-functional carboxylic acid anhydrides, saltsthereof and esters thereof. Such functional groups may be grafted to anethylene/α-olefin interpolymer, or it may be copolymerized with ethyleneand an optional additional comonomer to form an interpolymer ofethylene, the functional comonomer and optionally other comonomer(s).Means for grafting functional groups onto polyethylene are described forexample in U.S. Pat. Nos. 4,762,890, 4,927,888, and 4,950,541, thedisclosures of these patents are incorporated herein by reference intheir entirety. One particularly useful functional group is maleicanhydride.

The amount of the functional group present in the functionalinterpolymer can vary. The functional group can typically be present ina copolymer-type functionalized interpolymer in an amount of at leastabout 1.0 weight percent, preferably at least about 5 weight percent,and more preferably at least about 7 weight percent. The functionalgroup will typically be present in a copolymer-type functionalizedinterpolymer in an amount less than about 40 weight percent, preferablyless than about 30 weight percent, and more preferably less than about25 weight percent.

Processes Involving a Post-Reactor Heat Exchanger

The inventive reaction processes may be effective in virtually anyreaction which is capable of producing a metal alkyl compound, a metaloxide, or a mixture thereof and in which a post-reactor heat exchangeris employed. Such processes include solution processes for producingpolymers like polyolefins. In one embodiment, the invention is usefulfor producing a composition comprising virtually any polyolefin whichcomposition also comprises a metal alkyl compound, a metal oxide, or amixture thereof and in which a post-reactor heat exchanger is employed.Typical such polyolefins include homopolymers, copolymers, terpolymers,etc. formed from monomers like ethylene, propylene, butylene, etc. Theinventive processes may be useful in those reactions capable ofproducing propylene based plastomer or elastomer, preferably wherein theproduct comprises a propylene-ethylene interpolymer comprising at leastabout 80 mole percent propylene.

The processes have been found to be particularly effective in theproduction of the aforementioned inventive ethylene/α-olefin blockinterpolymers in which a chain shuttling agent such as diethyl zinc isemployed in the process. Such ethylene/α-olefin block interpolymers maybe characterized before any crosslinking by one or more of the followingcharacteristics:

(1) an average block index greater than zero and up to about 1.0 and amolecular weight distribution, Mw/Mn, greater than about 1.3; or

(2) at least one molecular fraction which elutes between 40° C. and 130°C. when fractionated using TREF, characterized in that the fraction hasa block index of at least 0.5 and up to about 1; or

(3) an Mw/Mn from about 1.7 to about 3.5, at least one melting point,Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter,wherein the numerical values of Tm and d correspond to the relationship:T _(m)>−6553.3+13735(d)−7051.7(d)²; or

(4) an Mw/Mn from about 1.7 to about 3.5, and a heat of fusion, ΔH inJ/g, and a delta quantity, ΔT, in degrees Celsius defined as thetemperature difference between the tallest DSC peak and the tallestCRYSTAF peak, wherein the numerical values of ΔT and ΔH have thefollowing relationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g,

wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or

(5) an elastic recovery, Re, in percent at 300 percent strain and 1cycle measured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenethylene/α-olefin interpolymer is substantially free of a cross-linkedphase:Re>1481−1629(d); or

(6) a molecular fraction which elutes between 40° C. and 130° C. whenfractionated using TREF, characterized in that the fraction has a molarcomonomer content of at least 5 percent higher than that of a comparablerandom ethylene interpolymer fraction eluting between the sametemperatures, wherein said comparable random ethylene interpolymer hasthe same comonomer(s) and has a melt index, density, and molar comonomercontent (based on the whole polymer) within 10 percent of that of theethylene/α-olefin interpolymer; or

(7) a storage modulus at 25° C., G′(25° C.), and a storage modulus at100° C., G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) isin the range of about 1:1 to about 9:1. The ethylene/α-olefin multiblockinterpolymer preferably comprise at least 50 mole percent ethylene.

As stated above, the processes have been found to be particularlyeffective in the production of the aforementioned inventiveethylene/α-olefin block interpolymers using a metal catalyst and/or achain shuttling agent. Suitable chain shuttling agents includediethylzinc, di(i-butyl)zinc, di(n-hexyl)zinc, triethylaluminum,trioctylaluminum, triethylgallium, i-butylaluminumbis(dimethyl(t-butyl)siloxane), i-butylaluminumbis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide),bis(n-octadecyl)i-butylaluminum, i-butylaluminum bis(di(n-pentyl)amide),n-octylaluminum bis(2,6-di-t-butylphenoxide, n-octylaluminumdi(ethyl(1-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide),ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), andethylzinc (t-butoxide). While not wishing to be bound to any particulartheory it is believed that the processes are particularly effective inprocesses employing a chain shuttling agent because the formation of thefoulant or discolorant is substantially reduced, hindered, or eveneliminated.

While not wishing to bound to any particular theory it is believed thatthe foulants may be produced in the following manner when employing, forexample, diethyl zinc. As the polymer leaves the reactor, much of thezinc is in the form of dipolymeryl zinc with two polymer chains per Znmolecule. The polymer may exit the reactor at a high temperature ofabout 140° C. or so and then become heated in, for example, acarbon-steel shell and tube post reactor heater (PRH) to from about 240to about 250° C. prior to devolatilization. Often, before the polymersolution enters the post reactor heater a catalyst kill agent and/orwater is added to deactivate any catalyst left in solution. The catalystkill agent must also deactivate the dipolymeryl zinc to produce a morestable Zn species before it reaches the PRH temperatures. Attemperatures above 140° C. dipolymeryl zinc, as with many metal alkylcompounds, is converted to a relatively insoluble zinc metal or zincoxide compound which subsequently results in fouling and/or discoloredpolymer product. It is hypothesized that this decomposition may occurthrough a free radical mechanism. The instant inventors discovered thatimprovements can be achieved by employing one or more of the followingfour steps:

(1) reacting said metal alkyl compound with an acid to produce a solublemetal ester; or

(2) adding an ionic surfactant; or

(3) adding a mixture comprising an antioxidant to the product underconditions sufficient to avoid formation of significant amounts ofinsoluble metal or metal compounds derived from said metal alkylcompound; or

(4) purging said post-reactor heat exchanger with an inert gas underconditions to remove metal oxide from the post-reactor heat exchanger.

Reacting Metal Alkyl Compound(s) with Acid

It has been discovered that one way to substantially reduce, hinder, oreven eliminate the majority of foulant of the PRH and/or discolorantfrom the product is by reacting any metal alkyl compound with a suitableacid to produce a soluble metal ester. The metal alkyl compounds mayvary depending upon the reactants and, if present, any catalyst and/orchain shuttling agent, as well as, the reaction conditions. Typically,the metal of the metal alkyl compound is a transition metal or GroupIIIA metal, or a combination thereof. Such metals often may includethose selected from the group consisting of zinc, aluminum, and gallium.The alkyl group may be branched or unbranched. The alkyl group may besubstituted or unsubstituted. Often, the alkyl group comprises apolymeric chain with a molecular weight of less than about 50,000although some metal alkyl may not be reacted which means that the alkylgroup may sometimes further comprise alkyl groups of about 2 carbons.Typically, the alkyl group comprises from about 2 to about 10,000 carbonatoms, preferably from about 1000 to about 5000 carbon atoms.

The acid is usually selected from those acids that are soluble in thereaction media employed. Suitable acids often include soluble carboxylicacids such as substituted or unsubstituted aliphatic metal ester.Suitable soluble carboxylic acids may comprise from about 6 to about 30carbon atoms and preferably are saturated or unsaturated aliphaticcarboxylic acids having from about 6 to about 20 carbon atoms such asstearic acid, octanoic acid, or a mixture thereof. Advantageously, theacid may be selected so that the soluble metal ester produced is suchthat it provides a desirable characteristic to the resulting product,i.e. one or more of the product properties are altered in a favorableway. That is one may employ a suitable acid such that the resultingsoluble metal ester is selected from the group consisting of anti-slipagents, mold release agents, nucleating agents, lubricating agents, andanti-fungal agents. In this manner, a desired additive to the productmay be produced in-situ. Desirable amounts of such agents would varydepending upon the application but would at least include an amount toperform the desired function, e.g., an anti-slipping effective amount,an anti-fungal effective amount, or a nucleating effective amount.

The reaction between metal alkyl compound with a suitable acid isconducted under suitable conditions to produce a soluble metal ester.These conditions may vary depending upon the specific metal alkylcompound, acid, and other compounds present. Advantageously, theconditions employed may simply be the conditions conventionally used toproduce the desired polymer product. Thus, if the desired product is,for example, an ethylene/α-olefin block interpolymer the conditionsnormally employed to produce said interpolymer may be employed and thesuitable acid may simply be added to the reactor after thepolymerization process or, more preferably, the suitable acid is addedto the reactor effluent as it leaves the reactor or shortly thereafter.

In any case it is often advantageous to add the acid, e.g., carboxylicacid, to the reaction prior to significant devolatization, e.g., priorto any significant post reactor heating, to more fully reduce, hinder,or even eliminate the majority of foulant of the PRH and/or discolorantfrom the interpolymer product. Also, it may be useful to mix the acidwith a solvent such as an isoparaffinic solvent like ISOPAR E™ beforereacting the acid with the heated metal alkyl compound. In this manner,the reaction to form a soluble metal ester is enhanced before saidproduct comprising the interpolymer product and metal ester is passed toa post-reactor heat exchanger. Often, the interpolymer product issubstantially free of metal oxide subsequent to the reaction of metalalkyl compound with an acid. This facilitates maintaining the heatexchange efficiency of the post reactor heat exchanger relativelyconstant over a longer time than if the acid had not been employed. Thatis, the efficiency drops less than about 2, preferably less than about1, preferably less than about 0.5% per day.

The molar ratio of acid such as carboxylic acid to metal may be anyconvenient ratio so long as the desired amount of the desired ester isproduced and/or the majority of foulant of the PRH and/or discolorantfrom the product is substantially reduced, hindered, or even eliminated.In many cases the desired ester and amount may be decided based upon howmuch one wishes to reduce or hinder the foulant of the PRH and/ordiscolorant from the product. That is, if one wishes to nearly eliminate(as opposed to just reduce) the foulant and/or discolorant, then onewill likely attempt to completely react the metal. Typically, the molarratio of acid to metal is from about 1:1 to about 10:1, preferably fromabout 1.25:1 to about 5:1, more preferably from about 1.5:1 to about3:1. It may be desirable to mix the acid with water before reacting itwith said metal alkyl compound if, for example, a soluble, complex metalester is desired. Such complex metal esters, for example, include thosehaving the formula Zn₄O(C_(n)H_(2n+1)CO₂)₆ wherein n is from about 5 toabout 20. In the case of complex metal esters, the acid may be mixedwith water in a molar ratio of acid to water of from about 10:1 to about0.5:1, preferably from about 4:1 to about 7:1. Alternatively, the amountof water may be from about 20 to about 30 times the amount of metal on amolar basis and/or the amount of water is from about 16 to about 22times the amount of acid on a molar basis. The useful specificmetal:H2O:acid ratios vary depending on the ingredients and often uponthe valency of the metal and ratio of metal to oxygen in the metaloxide. In the case of producing ethylene/α-olefin block interpolymersusing a zinc shuttling agent such as diethyl zinc it has been found thata particularly useful zinc:H₂O:acid ratio is about 1-2:24-26:1.4-1.6.

Adding an Ionic Surfactant

It has been discovered that another way to substantially reduce, hinder,or even eliminate the majority of foulant of the PRH and/or discolorantfrom the product is by adding an ionic surfactant to the reactor afterthe polymerization process or, more preferably, the ionic surfactant isadded to the reactor effluent as it leaves the reactor or shortlythereafter to form the desired product, e.g., ethylene/α-olefin blockinterpolymers. Advantageously, if the desired product is, for example,an ethylene/α-olefin block interpolymer, the conditions normallyemployed to produce said interpolymer may be employed and the suitableionic surfactant may simply be added to the reactor effluent as itleaves the reactor.

The ionic surfactant may vary depending upon the reactants and, ifpresent, any catalyst and/or chain shuttling agent, as well as, thereaction conditions. Typically, suitable ionic surfactants comprise apolar portion and a non-polar portion. Preferably, ionic surfactantscomprise a fatty acid salt such as those selected from the groupconsisting of alkali metal fatty acid salts, alkaline earth metal fattyacid salts, and mixtures thereof. A particularly preferable ionicsurfactant is a salt of stearic acid such as those selected from thegroup consisting of zinc stearate, calcium stearate, aluminum stearate,and mixtures thereof.

If desired, the ionic surfactant may be mixed with an effective amountof a suitable antistatic agent. Suitable antistatic agents and amountsvary widely depending upon the other ingredients. One suitableantistatic agent used when producing, for example, ethylene/α-olefinblock interpolymers, is an alkoxylated alkylamine such as ethoxylatedalkylamine. It has been found that a suitable amount of ethoxylatedalkylamine mixed with a salt of stearic acid may be particularlyeffective in substantially reducing, hindering, or even eliminating themajority of foulant of the PRH and/or discolorant when producing anethylene/α-olefin block interpolymer product.

The amount of ionic surfactant to be added varies depending upon thespecific metal, other compounds, and reaction conditions. Typically, themolar ratio of ionic surfactant to metal is from about 1:3 to about1:10, preferably from about 1:4 to about 1:6, more preferably about 1:5.On a mass basis the ratio of ionic surfactant to metal may be from about0.5:1 to about 10:1, more preferably from about 1.5:1 to about 3:1, morepreferably about 2:1. When ionic surfactant comprising a polar portionand a non-polar portion is added in these amounts, it has been foundthat the amount of deposits on the post reactor heat exchanger may bedecreased by a factor of at least five as compared to when an ionicsurfactant is not employed in the reaction process.

Adding a Mixture Comprising an Antioxidant

It has been discovered that another way to substantially reduce, hinder,or even eliminate the majority of foulant of the PRH and/or discolorantfrom the product is by adding a mixture comprising an antioxidant to theproduct under conditions sufficient to avoid formation of significantamounts, e.g., amounts that add visually observable color to theproduct, of insoluble metal or metal compounds derived from said metalalkyl compound.

Suitable antioxidants depend on the reactants and other products but formany polymer products such as ethylene/α-olefin block interpolymerssuitable antioxidants may often be selected from the group consisting ofsterically hindered phenols, sterically hindered phenyl phosphites, andmixtures thereof. Particularly preferable antioxidants are selected fromthe group consisting ofdi-octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate (such as IRGANOX1076), benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-,2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropo (suchas IRGANOX 1010), tertiary butyl phenyl phosphate (such as IRGAFOS 168),all of which are available from Ciba, and mixtures thereof.

The antioxidant may be mixed with other suitable compounds such as colorstabilizers such as hindered amines like 1,6-hexanediamine,N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-polymer with2,4,6-trichloro-1,3,5-triazine, reaction products withN-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine(such as CHIMASSORB 2020), N(C₁₈H₃₇)₂OH (such as IRGASTAB FS 042), allof which are available from Ciba and mixtures thereof. Other compoundsthat may be useful in admixture or separate from the antioxidant includecatalyst deactivators like deionized water, soluble protic quenchagents, e.g., methanol, isopropanol, or a mixture, solvents such asisoparaffinic solvents comprising mixed alkanes like ISOPAR E, andmixtures thereof.

The mixture comprising antioxidant and, if desired, one or more colorstabilizers, one or more catalyst deactivators, and/or one or moresolvents is added to the desired product under conditions sufficient toavoid formation of significant amounts of insoluble metal or metalcompounds derived from said metal alkyl compound. This may beaccomplished in any convenient manner. Typically, said mixture is addedto the product of said reaction process while passing said product to apost-reactor heat exchanger at an increased temperature. The increasedtemperature is usually below the vaporization temperature of thecomponents and varies by the process. For ethylene/α-olefin blockinterpolymer product the antioxidant may be added at a temperature offrom about 120° C. to about 200° C. In any event, the contacting may beaccomplished by employing one or more streams of antioxidant, colorstabilizer, catalyst deactivator, solvent, or any of the aforementionedseparately or combined at any convenient temperature and pressure.

The relative amount of antioxidant and, if desired, one or more colorstabilizers, one or more catalyst deactivators, and/or one or moresolvents varies depending upon the process. In general, the amount ofantioxidant, if any, varies depending upon the end use and requirementsof the final product. Similarly, the amount and type of colorstabilizer, if any, may vary depending upon the type of catalyst used.However, for ethylene/α-olefin block interpolymer product theantioxidant mixture typically comprises from about 0.2 to about 4.5,preferably from about 0.3 to about 3.5, weight percent antioxidant. Whencolor stabilizer is employed the mixture typically comprises from about0.2 to about 12, preferably from about 2 to about 11, weight percentcolor stabilizer.

Purging the Post-Reactor Heat Exchanger

Yet another way to substantially reduce, hinder, or even eliminate themajority of foulant in the PRH and/or discolorant from the product is byperiodically purging the PRH. Such a purge may be accomplished in anymanner but typically involves purging the post-reactor heat exchangerwith a gas selected from nitrogen, ethylene, or air. Advantageously,this, like the other steps, may be done alone or in combination with theother three steps. It has been found that often the purge is mosteffective when purging the post-reactor heat exchanger with nitrogenfirst in one direction and then in the other. This can be done as oftenas necessary.

Percolation Cleaning of a Fouled Heat Exchanger

Yet another way to substantially reduce, hinder, or even eliminate themajority of foulant in the PRH and/or discolorant from the product is toperiodically operate the heat exchanger at low pressure and/or hightemperature conditions to induce flashing conditions (e.g. one or moresolvents exceeds the boiling point). That is, boiling conditions areinduced preferably in a flowing viscous solution. In this manner foulingmaterials such as scale, polymer residues, inorganic deposits, organicdeposits, etc. may be reduced or removed from the surfaces of the heatexchanger (or any other pipe, valve, fitting, or vessel) via avapor-liquid separation or “percolation” type effect. In one embodiment,little or no additional materials (e.g., abrasives, special solvents, orreactive chemicals) need to be added to the flowing viscous solutionwhich often simply comprise one or more of the polymer product, solvent,and any by-products which may or may not include the foulants. Inanother embodiment, the conditions employed include inducing boilingover 50%, preferably more than 95% of the surface area of the equipment,e.g, surface of heat exchanger which may be subject to fouling.

The temperature, pressures, and time employed may vary depending uponthe specific product, equipment, and potential foulants. In someinstances it may be advantageous to employ conditions such that themelting point, e.g., crystallization temperature, of the polymer to beproduced is exceeded. Similarly, in some instances a rapiddepressurization, a pulsing of pressure, or other non-steady stateboiling conditions may facilitate the reduction or elimination of theone or more foulants.

Compositions of the Invention

Compositions of the present invention comprise an ethylene/α-olefinmultiblock interpolymer and a metal ester. Typically, theethylene/α-olefin multiblock interpolymer may be characterized beforeany crosslinking by one or more of the following characteristics:

(1) an average block index greater than zero and up to about 1.0 and amolecular weight distribution, Mw/Mn, greater than about 1.3; or

(2) at least one molecular fraction which elutes between 40° C. and 130°C. when fractionated using TREF, characterized in that the fraction hasa block index of at least 0.5 and up to about 1; or

(3) an Mw/Mn from about 1.7 to about 3.5, at least one melting point,Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter,wherein the numerical values of Tm and d correspond to the relationship:T _(n)>−6553.3+13735(d)−7051.7(d)²; or

(4) an Mw/Mn from about 1.7 to about 3.5, and a heat of fusion, ΔH inJ/g, and a delta quantity, ΔT, in degrees Celsius defined as thetemperature difference between the tallest DSC peak and the tallestCRYSTAF peak, wherein the numerical values of ΔT and ΔH have thefollowing relationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g,

wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or

(5) an elastic recovery, Re, in percent at 300 percent strain and 1cycle measured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenethylene/α-olefin interpolymer is substantially free of a cross-linkedphase:Re>1481−1629(d); or

(6) a molecular fraction which elutes between 40° C. and 130° C. whenfractionated using TREF, characterized in that the fraction has a molarcomonomer content of at least 5 percent higher than that of a comparablerandom ethylene interpolymer fraction eluting between the sametemperatures, wherein said comparable random ethylene interpolymer hasthe same comonomer(s) and has a melt index, density, and molar comonomercontent (based on the whole polymer) within 10 percent of that of theethylene/α-olefin interpolymer; or

(7) a storage modulus at 25° C., G′(25° C.), and a storage modulus at100° C., G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) isin the range of about 1:1 to about 9:1.

The metal ester varies depending upon the desired characteristics of thecomposition but typically is a substituted or unsubstituted aliphaticmetal ester. The metal ester preferably comprises from about 6 to about30 carbon atoms. In one embodiment the substituted or unsubstitutedaliphatic group is dependent upon the type of acid that may be employedas a catalyst deactivator. For example, if hexanoic acid is employed,then a C6 metal ester results while stearic acid may yield a C16 metalester. The metal of the metal ester is a transition metal, Group IIAmetal, Group IIIA metal, or a combination thereof. Preferably, the metalof the metal ester is selected from the group consisting of calcium,zinc, aluminum, and gallium. Particularly preferable metal estersinclude a metal stearate such as zinc stearate or calcium stearate, ametal octanoate such as zinc octanoate, or a mixture thereof.

The compositions may be made using the methods employed above whereinbefore, during, or subsequent to the production of the ethylene/α-olefinmultiblock interpolymer, a metal alkyl compound is reacted with an acidto produce a soluble metal ester. Alternatively, the metal ester andethylene/α-olefin multiblock interpolymer may be simply mixed in anyconvenient manner. Advantageously, when made by reacting the metal alkylcompound with an acid, the resulting compositions are oftensubstantially free of metal oxides such as zinc oxides. This means thatin many cases the compositions comprise less than about 100, preferablyless than 50, more preferably less than 10 ppm of metal oxide based onthe weight of the composition. A relatively low amount of metal oxide inthe composition often reduces fouling of the PRH and may result in awhiter or less yellowed interpolymer product. Preferably, the resultingproduct in one embodiment has a whiteness index from above 50,preferably from about 50 to about 100, more preferably above about 70.In another embodiment, the resulting product has a yellowness index offrom about 5 to about −30, preferably from about −1 to −15, morepreferably less than about −2 according to ASTM D6290-05. In yet anotherembodiment, the resulting product has both a whiteness index andyellowness index within the aforementioned ranges.

The amount of a metal ester in the composition can vary depending uponthe desired use of the composition and the desired role and type of themetal ester. That is, if the metal ester is employed as an anti-slipagent then it should be present in an anti-slipping effective amount.Similarly, if the metal ester is to be employed as an anti-fungal agentor nucleacting agent, then it should be present in an anti-fungaleffective amount or nucleating effective amount, respectively.Typically, for most uses the metal ester need only be present in smallamounts of less than about 3 weight percent. Preferably in most cases,the metal ester is present in an amount of from about 10 ppm to about10,000 ppm, or from about 50 ppm to about 5,000 ppm, or from about 1000ppm to about 2500 ppm, or from about 200 to about 1000 ppm, based on thetotal weight of the composition.

The aforementioned compositions may be blended with one or more suitableadditional polymers during the production of ethylene/α-olefinmultiblock interpolymer or subsequently. Suitable polymers include, forexample, a propylene based plastomer or elastomer, random ethylenecopolymers such as AFFINITY® or ENGAGE®, traditional polyethylenes suchas HDPE, LLDPE, ULDPE, LDPE and propylene-based polymers such ashomopolymer PP, random copolymer PP or PP-based plastomers/elastomers ora combination thereof. The amount of such other polymers differsdepending upon the desired properties and compatibility with thespecific ethylene/α-olefin interpolymer and metal ester employed.

Useful propylene based plastomers or elastomers include polypropylenesformed by any means within the skill in the art. The propylene andoptional comonomers, such as ethylene or alpha-olefin monomers arepolymerized under conditions within the skill in the art, for instance,as disclosed by Galli, et al., Angew. Macromol. Chem., Vol. 120, 73(1984), or by E. P. Moore, et al. in Polypropylene Handbook, HanserPublishers, New York, 1996, particularly pages 11-98. Polypropylenepolymers include Solvay's KS 4005 polypropylene copolymer; Solvay's KS300 polypropylene terpolymer; and INSPIRE™ polymers and VERSIFY™polymers, both available from The Dow Chemical Company. Suitablebranched propylene-based polymers for use in the present invention arecommercially available, for instance from Montell North America, underthe trade designations Profax PF-611 and PF-814. Alternatively, suitablebranched or coupled propylene-based polymers can be prepared by meanswithin the skill in the art, such as by peroxide or electron-beamtreatment, for instance as disclosed by DeNicola et al., in U.S. Pat.No. 5,414,027 (the use of high energy (ionizing) radiation in a reducedoxygen atmosphere); EP 0 190 889 to Himont (electron beam irradiation ofisotactic polypropylene at lower temperatures); U.S. Pat. No. 5,464,907(Akzo Nobel NV); EP 0 754 711 Solvay (peroxide treatment); and U.S.patent application Ser. No. 09/133,576, filed Aug. 13, 1998 (azidecoupling agents). Each of these patents/applications is incorporatedherein by reference.

Other particularly suitable propylene-based polymers include VERSIFY™polymers (The Dow Chemical Company) and VISTAMAXX™ polymers (ExxonMobilChemical Co.), LICOCENE™ polymers (Clariant), EASTOFLEX™ polymers(Eastman Chemical Co.), REXTAC™ polymers (Hunstman), and VESTOPLAST™polymers (Degussa). Other suitable polymers include propylene-α-olefinsblock copolymers and interpolymers, and other propylene based blockcopolymers and interpolymers known in the art.

REPRESENTATIVE EMBODIMENTS OF THE INVENTION

The following embodiments are representative specific embodiments of theinstant invention.

1. In a reaction process which comprises reacting a mixture via areaction to form at least one product comprising a metal alkyl compound,a metal oxide, or a mixture thereof and then passing said product to atleast one post-reactor heat exchanger, the improvement which comprisesone or more of the following steps:

(1) reacting said metal alkyl compound with an acid to produce a solublemetal ester; or

(2) adding an ionic surfactant after the reaction to form at least oneproduct comprising a metal alkyl compound, a metal oxide, or a mixturethereof; or

(3) adding a mixture comprising an antioxidant to the product underconditions sufficient to avoid formation of significant amounts ofinsoluble metal or metal compounds derived from said metal alkylcompound; or

(4) purging said post-reactor heat exchanger with an inert gas underconditions to remove metal oxide from the post-reactor heat exchanger.

2. The reaction process of claim 1 wherein the product comprises apolymer.

3. The reaction process of one or more of the preceding claims whereinthe product comprises a polyolefin.

4. The reaction process of one or more of the preceding claims whereinthe product comprises a polyolefin selected from the group consisting ofpolyethylenes, polypropylenes, polybutylenes, and mixtures thereof.

5. The reaction process of one or more of the preceding claims whereinthe product comprises an a propylene based plastomer or elastomer.

6. The reaction process of one or more of the preceding claims whereinthe product comprises an a propylene-ethylene interpolymer comprising atleast about 80 mole percent propylene.

7. The reaction process of one or more of the preceding claims whereinthe product comprises an

ethylene/α-olefin multiblock interpolymer.

8. The reaction process of one or more of the preceding claims whereinthe product comprises an

ethylene/α-olefin multiblock interpolymer which is characterized beforeany crosslinking by one or more of the following characteristics:

(1) an average block index greater than zero and up to about 1.0 and amolecular weight distribution, Mw/Mn, greater than about 1.3; or

(2) at least one molecular fraction which elutes between 40° C. and 130°C. when fractionated using TREF, characterized in that the fraction hasa block index of at least 0.5 and up to about 1; or

(3) an Mw/Mn from about 1.7 to about 3.5, at least one melting point,Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter,wherein the numerical values of Tm and d correspond to the relationship:T _(m)>−6553.3+13735(d)−7051.7(d)²; or

(4) an Mw/Mn from about 1.7 to about 3.5, and a heat of fusion, ΔH inJ/g, and a delta quantity, ΔT, in degrees Celsius defined as thetemperature difference between the tallest DSC peak and the tallestCRYSTAF peak, wherein the numerical values of ΔT and ΔH have thefollowing relationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g,

wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or

(5) an elastic recovery, Re, in percent at 300 percent strain and 1cycle measured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenethylene/α-olefin interpolymer is substantially free of a cross-linkedphase:Re>1481−1629(d); or

(6) a molecular fraction which elutes between 40° C. and 130° C. whenfractionated using TREF, characterized in that the fraction has a molarcomonomer content of at least 5 percent higher than that of a comparablerandom ethylene interpolymer fraction eluting between the sametemperatures, wherein said comparable random ethylene interpolymer hasthe same comonomer(s) and has a melt index, density, and molar comonomercontent (based on the whole polymer) within 10 percent of that of theethylene/α-olefin interpolymer; or

(7) a storage modulus at 25° C., G′(25° C.), and a storage modulus at100° C., G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) isin the range of about 1:1 to about 9:1.

9. The reaction process of one or more of the preceding claims whereinthe product comprises an

ethylene/α-olefin multiblock interpolymer comprising at least 50 molepercent ethylene.

10. The reaction process of one or more of the preceding claims whereinthe process comprises employing a catalyst comprising a metal.

11. The reaction process of one or more of the preceding claims whereinthe process comprises employing a shuttling agent.

12. The reaction process of one or more of the preceding claims whereinthe process comprises employing a shuttling agent selected from thegroup consisting of diethylzinc, di(i-butyl)zinc, di(n-hexyl)zinc,triethylaluminum, trioctylaluminum, triethylgallium, i-butylaluminumbis(dimethyl(t-butyl)siloxane), i-butylaluminumbis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide),bis(n-octadecyl)i-butylaluminum, butylaluminum bis(di(n-pentyl)amide),n-octylaluminum bis(2,6-di-t-butylphenoxide, n-octylaluminumdi(ethyl(1-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide),ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), andethylzinc (t-butoxide).13. The reaction process of one or more of the preceding claims whereinthe metal oxide is zinc oxide.14. The reaction process of one or more of the preceding claims whereinthe metal alkyl compound is reacted with an acid selected from the groupconsisting of soluble carboxylic acids under conditions sufficient toproduce a soluble metal ester.15. The reaction process of one or more of the preceding claims whereinthe soluble carboxylic acid is a substituted or unsubstituted aliphaticmetal ester.16. The reaction process of one or more of the preceding claims whereinthe soluble carboxylic acid comprises from about 6 to about 30 carbonatoms.17. The reaction process of one or more of the preceding claims whereinthe metal of the metal alkyl compound is a transition metal or GroupIIIA metal, or a combination thereof.18. The reaction process of one or more of the preceding claims whereinthe metal of the metal alkyl compound is selected from the groupconsisting of zinc, aluminum, and gallium.19. The reaction process of one or more of the preceding claims whereinthe soluble carboxylic acid is a saturated or unsaturated aliphaticcarboxylic acid having from about 6 to about 20 carbon atoms.20. The reaction process of one or more of the preceding claims whereinthe soluble carboxylic acid is stearic acid, octanoic acid, or a mixturethereof.21. The reaction process of one or more of the preceding claims whereinsubsequent to the reaction of metal alkyl compound with an acid theproduct is substantially free of metal oxide.22. The reaction process of one or more of the preceding claims whereinthe soluble metal ester produced is selected such that it provides adesirable characteristic to the resulting product.23. The reaction process of one or more of the preceding claims whereinthe soluble metal ester is selected from the group consisting ofanti-slip agents, mold release agents, nucleating agents, lubricatingagents, and anti-fungal agents.24. The reaction process of one or more of the preceding claims whereinthe carboxylic acid is added to the reaction prior to significantdevolatization.25. The reaction process of one or more of the preceding claims whereinthe molar ratio of carboxylic acid to metal is from about 1:1 to about10:1.26. The reaction process of one or more of the preceding claims whereinthe molar ratio of carboxylic acid to metal is from about 1.5:1 to about3:1.27. The reaction process of one or more of the preceding claims whereinthe carboxylic acid is mixed with water before reacting it with saidmetal alkyl compound and wherein the resulting soluble metal ester is acomplex metal ester.28. The reaction process of one or more of the preceding claims whereinthe carboxylic acid is mixed with water in a molar ratio of carboxylicacid to water of from about 10:1 to about 0.5:1.29. The reaction process of one or more of the preceding claims whereinthe amount of water is from about 20 to about 30 times the amount ofmetal on a molar basis and the amount of water is from about 16 to about22 times the amount of carboxylic acid on a molar basis.30. The reaction process of one or more of the preceding claims whereinthe molar ratio of carboxylic acid is mixed with water in a molar ratioof carboxylic acid to water of from about 4:1 to about 7:1.31. The reaction process of one or more of the preceding claims whereinthe resulting soluble metal ester is a complex metal ester having theformula Zn₄O(C_(n)H_(2n+1)CO₂)₆ wherein n is from about 5 to about 20.32. The reaction process of one or more of the preceding claims whereinthe acid is mixed with an isoparaffinic solvent before reacting it witha heated metal alkyl compound to produce a soluble metal ester and thenpassing said product to a post-reactor heat exchanger.33. The reaction process of one or more of the preceding claims whereinthe heat exchange efficiency of the post reactor heat exchanger remainsrelatively constant over time.34. The reaction process of one or more of the preceding claims whereinan ionic surfactant comprising a polar portion and a non-polar portionis added after the reaction.35. The reaction process of one or more of the preceding claims whereinthe ionic surfactant comprises a fatty acid salt.36. The reaction process of one or more of the preceding claims whereinthe ionic surfactant comprises a fatty acid salt selected from the groupconsisting of alkali metal fatty acid salts, alkaline earth metal fattyacid salts, and mixtures thereof.37. The reaction process of one or more of the preceding claims whereinthe ionic surfactant is a salt of stearic acid.38. The reaction process of one or more of the preceding claims whereinthe ionic surfactant is selected from the group consisting of zincstearate, calcium stearate, aluminum stearate, and mixtures thereof.39. The reaction process of one or more of the preceding claims whereinthe ionic surfactant is mixed with an effective amount of antistaticagent.40. The reaction process of one or more of the preceding claims whereinthe antistatic agent is an alkoxylated alkylamine.41. The reaction process of one or more of the preceding claims whereinthe antistatic agent is an ethoxylated alkylamine.42. The reaction process of one or more of the preceding claims whereinthe molar ratio of ionic surfactant to metal is at least about 1:3.43. The reaction process of one or more of the preceding claims whereinthe molar ratio of ionic surfactant to metal is from about 1:3 to about1:10.44. The reaction process of one or more of the preceding claims whereinthe ratio of ionic surfactant to metal is from about 0.5:1 to about 10:1on a mass basis.44. The reaction process of one or more of the preceding claims whereinthe amount of deposits on the post reactor heat exchanger is decreasedby a factor of at least five when an ionic surfactant comprising a polarportion and a non-polar portion is added as compared to when an ionicsurfactant is not employed.45. The reaction process of one or more of the preceding claimscomprising adding a mixture comprising an antioxidant selected from thegroup consisting of sterically hindered phenols, sterically hinderedphenyl phosphites, and mixtures thereof to the product under conditionssufficient to avoid formation of significant amounts of insoluble metalor metal compounds derived from said metal alkyl compound.46. The reaction process of one or more of the preceding claims whereinthe antioxidant is selected from the group consisting ofdi-octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, benzenepropanoicacid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-,2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropo,tertiary butyl phenyl phosphate, and mixtures thereof.47. The reaction process of one or more of the preceding claims whereinthe antioxidant is mixed with a color stabilizer, a catalystdeactivator, a solvent, or a mixture thereof.48. The reaction process of one or more of the preceding claims whereinthe color stabilizer is a hindered amine.49. The reaction process of one or more of the preceding claims whereinthe color stabilizer is 1,6-hexanediamine,N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-polymer with2,4,6-trichloro-1,3,5-triazine, reaction products withN-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine,N(C₁₈H₃₇)₂OH, and mixtures thereof.50. The reaction process of one or more of the preceding claims whereinthe solvent is an isoparaffinic solvent comprising mixed alkanes.51. The reaction process of one or more of the preceding claims whereinthe catalyst deactivator is selected from the group consisting ofdeionized water, soluble protic quench agents, and mixtures thereof.52. The reaction process of one or more of the preceding claims whereinthe soluble protic quench agent is selected from the group consisting ofmethanol, isopropanol, and mixtures thereof.53. The reaction process of one or more of the preceding claims whereina mixture comprising antioxidant, color stabilizer, and solvent iscontacted with a product of said reaction process while passing saidproduct to a post-reactor heat exchanger.54. The reaction process of one or more of the preceding claims whereina mixture comprising antioxidant, color stabilizer, catalystdeactivator, and solvent is contacted with a product of said reactionprocess while passing said product to a post-reactor heat exchanger.55. The reaction process of one or more of the preceding claims whereinan antioxidant, color stabilizer, catalyst deactivator, and solvent arecontacted with a product of said reaction process while passing saidproduct to a post-reactor heat exchanger.56. The reaction process of one or more of the preceding claims whereinan antioxidant, color stabilizer, catalyst deactivator, and solvent arecontacted with a product of said reaction process while passing saidproduct to a post-reactor heat exchanger and said contacting isaccomplished by one or more streams of antioxidant, color stabilizer,catalyst deactivator, solvent, or mixtures thereof.57. The reaction process of one or more of the preceding claims whereina mixture comprising antioxidant, color stabilizer, and solvent iscontacted with a product of said reaction process while passing saidproduct to a post-reactor heat exchanger wherein said mixture comprisesfrom about 0.2 to about 4.5 weight percent antioxidant.58. The reaction process of one or more of the preceding claims whereina mixture comprising antioxidant, color stabilizer, and solvent iscontacted with a product of said reaction process while passing saidproduct to a post-reactor heat exchanger wherein said mixture comprisesfrom about 0.3 to about 3.5 weight percent antioxidant.59. The reaction process of one or more of the preceding claims whereina mixture comprising antioxidant, color stabilizer, and solvent iscontacted with a product of said reaction process while passing saidproduct to a post-reactor heat exchanger wherein said mixture comprisesfrom about 0.2 to about 12 weight percent color stabilizer.60. The reaction process of one or more of the preceding claims whereina mixture comprising antioxidant, color stabilizer, and solvent iscontacted with a product of said reaction process while passing saidproduct to a post-reactor heat exchanger wherein said mixture comprisesfrom about 2 to about 11 weight percent color stabilizer.61. The reaction process of one or more of the preceding claims whereinthe mixture comprising antioxidant is added at a temperature of fromabout 120° C. to about 200° C.62. The reaction process of one or more of the preceding claims whichcomprises purging the post-reactor heat exchanger with a gas selectedfrom nitrogen, ethylene, or air.63. The reaction process of one or more of the preceding claims whichcomprises purging the post-reactor heat exchanger with nitrogen first inone direction and then in the other.64. A composition comprising an ethylene/α-olefin multiblockinterpolymer and a metal ester.65. The composition of one or more of the preceding claims wherein themetal ester is a substituted or unsubstituted aliphatic metal ester.66. The composition of one or more of the preceding claims wherein themetal ester comprises from about 6 to about 30 carbon atoms.67. The composition of one or more of the preceding claims wherein themetal of the metal ester is a transition metal or Group IIIA metal, or acombination thereof.68. The composition of one or more of the preceding claims wherein themetal of the metal ester is selected from the group consisting of zinc,aluminum, and gallium.69. The composition of one or more of the preceding claims wherein themetal ester is a metal stearate, a metal octanoate, or a mixturethereof.70. The composition of one or more of the preceding claims wherein themetal ester is zinc stearate, zinc octanoate, or a mixture thereof.71. The composition of one or more of the preceding claims wherein thecomposition is substantially free of metal oxide.72. The composition of one or more of the preceding claims wherein thecomposition is substantially free of zinc oxide.73. The composition of one or more of the preceding claims wherein thecomposition comprises less than about 100 ppm of metal oxide based onthe weight of the composition.74. The composition of one or more of the preceding claims wherein thecomposition comprises less than about 50 ppm of metal oxide based on theweight of the composition.75. The composition of one or more of the preceding claims wherein thecomposition comprises less than about 10 ppm of metal oxide based on theweight of the composition.76. The composition of one or more of the preceding claims wherein themetal ester is present in an anti-slipping effective amount.77. The composition of one or more of the preceding claims wherein themetal ester is present in an anti-fungal effective amount.78. The composition of one or more of the preceding claims wherein themetal ester is present in a nucleating effective amount.79. The composition of one or more of the preceding claims wherein themetal ester is present in an amount of from about 10 ppm to about 10,000ppm based on the total weight of the composition.80. The composition of one or more of the preceding claims wherein themetal ester is present in an amount of from about 50 to about 5,000 ppmbased on the total weight of the composition.81. The composition of one or more of the preceding claims wherein themetal ester is present in an amount of from about 1000 to about 2500 ppmbased on the total weight of the composition.82. The composition of one or more of the preceding claims wherein theresulting product has a whiteness index above 50.83. The composition of one or more of the preceding claims wherein theresulting product has a yellowness index less than −2.Testing Methods

In the examples that follow, the following analytical techniques areemployed:

GPC Method for Samples 1-4 and A-C

An automated liquid-handling robot equipped with a heated needle set to160° C. is used to add enough 1,2,4-trichlorobenzene stabilized with 300ppm Ionol to each dried polymer sample to give a final concentration of30 mg/mL. A small glass stir rod is placed into each tube and thesamples are heated to 160° C. for 2 hours on a heated, orbital-shakerrotating at 250 rpm. The concentrated polymer solution is then dilutedto 1 mg/ml using the automated liquid-handling robot and the heatedneedle set to 160° C.

A Symyx Rapid GPC system is used to determine the molecular weight datafor each sample. A Gilson 350 pump set at 2.0 ml/min flow rate is usedto pump helium-purged 1,2-dichlorobenzene stabilized with 300 ppm lonolas the mobile phase through three Plgel 10 micrometer (μm) Mixed B 300mm×7.5 mm columns placed in series and heated to 160° C. A Polymer LabsELS 1000 Detector is used with the Evaporator set to 250° C., theNebulizer set to 165° C., and the nitrogen flow rate set to 1.8 SLM at apressure of 60-80 psi (400−600 kPa) N₂. The polymer samples are heatedto 160° C. and each sample injected into a 250 μl loop using theliquid-handling robot and a heated needle. Serial analysis of thepolymer samples using two switched loops and overlapping injections areused. The sample data is collected and analyzed using Symyx Epoch™software. Peaks are manually integrated and the molecular weightinformation reported uncorrected against a polystyrene standardcalibration curve.

Standard CRYSTAF Method

Branching distributions are determined by crystallization analysisfractionation (CRYSTAF) using a CRYSTAF 200 unit commercially availablefrom PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4trichlorobenzene at 160° C. (0.66 mg/mL) for 1 hr and stabilized at 95°C. for 45 minutes. The sampling temperatures range from 95 to 30° C. ata cooling rate of 0.2° C./min. An infrared detector is used to measurethe polymer solution concentrations. The cumulative solubleconcentration is measured as the polymer crystallizes while thetemperature is decreased. The analytical derivative of the cumulativeprofile reflects the short chain branching distribution of the polymer.

The CRYSTAF peak temperature and area are identified by the peakanalysis module included in the CRYSTAF Software (Version 2001.b,PolymerChar, Valencia, Spain). The CRYSTAF peak finding routineidentifies a peak temperature as a maximum in the dW/dT curve and thearea between the largest positive inflections on either side of theidentified peak in the derivative curve. To calculate the CRYSTAF curve,the preferred processing parameters are with a temperature limit of 70°C. and with smoothing parameters above the temperature limit of 0.1, andbelow the temperature limit of 0.3.

DSC Standard Method (Excluding Samples 1-4 and A-C)

Differential Scanning calorimetry results are determined using a TAImodel Q1000 DSC equipped with an RCS cooling accessory and anautosampler. A nitrogen purge gas flow of 50 ml/min is used. The sampleis pressed into a thin film and melted in the press at about 175° C. andthen air-cooled to room temperature (25° C.). 3-10 mg of material isthen cut into a 6 mm diameter disk, accurately weighed, placed in alight aluminum pan (ca 50 mg), and then crimped shut. The thermalbehavior of the sample is investigated with the following temperatureprofile. The sample is rapidly heated to 180° C. and held isothermal for3 minutes in order to remove any previous thermal history. The sample isthen cooled to −40° C. at 10° C./min cooling rate and held at −40° C.for 3 minutes. The sample is then heated to 150° C. at 10° C./min.heating rate. The cooling and second heating curves are recorded.

The DSC melting peak is measured as the maximum in heat flow rate (W/g)with respect to the linear baseline drawn between −30° C. and end ofmelting. The heat of fusion is measured as the area under the meltingcurve between −30° C. and the end of melting using a linear baseline.

GPC Method (Excluding Samples 1-4 and A-C)

The gel permeation chromatographic system consists of either a PolymerLaboratories Model PL-210 or a Polymer Laboratories Model PL-220instrument. The column and carousel compartments are operated at 140° C.Three Polymer Laboratories 10-micron Mixed-B columns are used. Thesolvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000, and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci., Polym.Let., 6, 621 (1968)): M_(polyethylene)=0.431(M_(polystyrene))

Polyethylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software Version 3.0.

Compression Set

Compression set is measured according to ASTM D 395. The sample isprepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm, and0.25 mm thickness until a total thickness of 12.7 mm is reached. Thediscs are cut from 12.7 cm×12.7 cm compression molded plaques moldedwith a hot press under the following conditions: zero pressure for 3 minat 190° C., followed by 86 MPa for 2 min at 190° C., followed by coolinginside the press with cold running water at 86 MPa.

Density

Samples for density measurement are prepared according to ASTM D 1928.Measurements are made within one hour of sample pressing using ASTMD792, Method B.

Flexural/Secant Modulus/Storage Modulus

Samples are compression molded using ASTM D 1928. Flexural and 2 percentsecant moduli are measured according to ASTM D-790. Storage modulus ismeasured according to ASTM D 5026-01 or equivalent technique.

Optical Properties

Films of 0.4 mm thickness are compression molded using a hot press(Carver Model #4095-4PR1001R). The pellets are placed betweenpolytetrafluoroethylene sheets, heated at 190° C. at 55 psi (380 kPa)for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min.The film is then cooled in the press with running cold water at 1.3 MPafor 1 min. The compression molded films are used for opticalmeasurements, tensile behavior, recovery, and stress relaxation.

Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D1746.

45° gloss is measured using BYK Gardner Glossmeter Microgloss 45° asspecified in ASTM D-2457

Internal haze is measured using BYK Gardner Haze-gard based on ASTM D1003 Procedure A. Mineral oil is applied to the film surface to removesurface scratches.

Mechanical Properties—Tensile, Hysteresis, and Tear

Stress-strain behavior in uniaxial tension is measured using ASTM D 1708microtensile specimens. Samples are stretched with an Instron at 500%min⁻¹ at 21° C. Tensile strength and elongation at break are reportedfrom an average of 5 specimens.

100% and 300% Hysteresis is determined from cyclic loading to 100% and300% strains using ASTM D 1708 microtensile specimens with an Instron™instrument. The sample is loaded and unloaded at 267% min⁻¹ for 3 cyclesat 21° C. Cyclic experiments at 300% and 80° C. are conducted using anenvironmental chamber. In the 80° C. experiment, the sample is allowedto equilibrate for 45 minutes at the test temperature before testing. Inthe 21° C., 300% strain cyclic experiment, the retractive stress at 150%strain from the first unloading cycle is recorded. Percent recovery forall experiments are calculated from the first unloading cycle using thestrain at which the load returned to the base line. The percent recoveryis defined as:

${\%\mspace{14mu}{Recovery}} = {\frac{ɛ_{f} - ɛ_{s}}{ɛ_{f}} \times 100}$where ε_(f) is the strain taken for cyclic loading and ε_(s) is thestrain where the load returns to the baseline during the 1^(st)unloading cycle.

Stress relaxation is measured at 50 percent strain and 37° C. for 12hours using an Instron™ instrument equipped with an environmentalchamber. The gauge geometry was 76 mm×25 mm×0.4 mm. After equilibratingat 37° C. for 45 min in the environmental chamber, the sample wasstretched to 50% strain at 333% min⁻¹. Stress was recorded as a functionof time for 12 hours. The percent stress relaxation after 12 hours wascalculated using the formula:

${\%\mspace{14mu}{Stress}\mspace{14mu}{Relaxation}} = {\frac{L_{0} - L_{12}}{L_{0}} \times 100}$where L₀ is the load at 50% strain at 0 time and L₁₂ is the load at 50percent strain after 12 hours.

Tensile notched tear experiments are carried out on samples having adensity of 0.88 g/cc or less using an Instron™ instrument. The geometryconsists of a gauge section of 76 mm×13 mm×0.4 mm with a 2 mm notch cutinto the sample at half the specimen length. The sample is stretched at508 mm min⁻¹ at 21° C. until it breaks. The tear energy is calculated asthe area under the stress-elongation curve up to strain at maximum load.An average of at least 3 specimens are reported.

TMA

Thermal Mechanical Analysis (Penetration Temperature) is conducted on 30mm diameter×3.3 mm thick, compression molded discs, formed at 180° C.and 10 MPa molding pressure for 5 minutes and then air quenched. Theinstrument used is a TMA 7, brand available from Perkin-Elmer. In thetest, a probe with 1.5 mm radius tip (P/N N519-0416) is applied to thesurface of the sample disc with 1N force. The temperature is raised at5° C./min from 25° C. The probe penetration distance is measured as afunction of temperature. The experiment ends when the probe haspenetrated 1 mm into the sample.

DMA

Dynamic Mechanical Analysis (DMA) is measured on compression moldeddisks formed in a hot press at 180° C. at 10 MPa pressure for 5 minutesand then water cooled in the press at 90° C./min. Testing is conductedusing an ARES controlled strain rheometer (TA instruments) equipped withdual cantilever fixtures for torsion testing.

A 1.5 mm plaque is pressed and cut in a bar of dimensions 32×12 mm. Thesample is clamped at both ends between fixtures separated by 10 mm (gripseparation ΔL) and subjected to successive temperature steps from −100°C. to 200° C. (5° C. per step). At each temperature the torsion modulusG′ is measured at an angular frequency of 10 rad/s, the strain amplitudebeing maintained between 0.1 percent and 4 percent to ensure that thetorque is sufficient and that the measurement remains in the linearregime.

An initial static force of 10 g is maintained (auto-tension mode) toprevent slack in the sample when thermal expansion occurs. As aconsequence, the grip separation ΔL increases with the temperature,particularly above the melting or softening point of the polymer sample.The test stops at the maximum temperature or when the gap between thefixtures reaches 65 mm.

Melt Index

Melt index, or I₂, is measured in accordance with ASTM D 1238, Condition190° C./2.16 kg. Melt index, or I₁₀ is also measured in accordance withASTM D 1238, Condition 190° C./10 kg.

ATREF

Analytical temperature rising elution fractionation (ATREF) analysis isconducted according to the method described in U.S. Pat. No. 4,798,081and Wilde, L.; Ryle, T. R.; Knobeloch, D. C.; Peat, I. R.; Determinationof Branching Distributions in Polyethylene and Ethylene Copolymers, J.Polym. Sci., 20, 441-455 (1982), which are incorporated by referenceherein in their entirety. The composition to be analyzed is dissolved intrichlorobenzene and allowed to crystallize in a column containing aninert support (stainless steel shot) by slowly reducing the temperatureto 20° C. at a cooling rate of 0.1° C./min. The column is equipped withan infrared detector. An ATREF chromatogram curve is then generated byeluting the crystallized polymer sample from the column by slowlyincreasing the temperature of the eluting solvent (trichlorobenzene)from 20 to 120° C. at a rate of 1.5° C./min.

¹³C NMR Analysis

The samples are prepared by adding approximately 3 g of a 50/50 mixtureof tetrachloroethane-d²/orthodichlorobenzene to 0.4 g sample in a 10 mmNMR tube. The samples are dissolved and homogenized by heating the tubeand its contents to 150° C. The data are collected using a JEOL Eclipse™400 MHz spectrometer or a Varian Unity Plus™ 400 MHz spectrometer,corresponding to a ¹³C resonance frequency of 100.5 MHz. The data areacquired using 4000 transients per data file with a 6 second pulserepetition delay. To achieve minimum signal-to-noise for quantitativeanalysis, multiple data files are added together. The spectral width is25,000 Hz with a minimum file size of 32K data points. The samples areanalyzed at 130° C. in a 10 mm broad band probe. The comonomerincorporation is determined using Randall's triad method (Randall, J.C.; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989), which isincorporated by reference herein in its entirety.

Polymer Fractionation by TREF

Large-scale TREF fractionation is carried by dissolving 15-20 g ofpolymer in 2 liters of 1,2,4-trichlorobenzene (TCB) by stirring for 4hours at 160° C. The polymer solution is forced by 15 psig (100 kPa)nitrogen onto a 3 inch by 4 foot (7.6 cm×12 cm) steel column packed witha 60:40 (v:v) mix of 30-40 mesh (600-425 μm) spherical, technicalquality glass beads (available from Potters Industries, HC 30 Box 20,Brownwood, Tex., 76801) and stainless steel, 0.028″ (0.7 mm) diametercut wire shot (available from Pellets, Inc. 63 Industrial Drive, NorthTonawanda, N.Y., 14120). The column is immersed in a thermallycontrolled oil jacket, set initially to 160° C. The column is firstcooled ballistically to 125° C., then slow cooled to 20° C. at 0.04° C.per minute and held for one hour. Fresh TCB is introduced at about 65ml/min while the temperature is increased at 0.167° C. per minute.

Approximately 2000 ml portions of eluant from the preparative TREFcolumn are collected in a 16 station, heated fraction collector. Thepolymer is concentrated in each fraction using a rotary evaporator untilabout 50 to 100 ml of the polymer solution remains. The concentratedsolutions are allowed to stand overnight before adding excess methanol,filtering, and rinsing (approx. 300-500 ml of methanol including thefinal rinse). The filtration step is performed on a 3 position vacuumassisted filtering station using 5.0 μm polytetrafluoroethylene coatedfilter paper (available from Osmonics Inc., Cat# Z50WPO4750). Thefiltrated fractions are dried overnight in a vacuum oven at 60° C. andweighed on an analytical balance before further testing.

Melt Strength

Melt Strength (MS) is measured by using a capillary rheometer fittedwith a 2.1 mm diameter, 20:1 die with an entrance angle of approximately45 degrees. After equilibrating the samples at 190° C. for 10 minutes,the piston is run at a speed of 1 inch/minute (2.54 cm/minute). Thestandard test temperature is 190° C. The sample is drawn uniaxially to aset of accelerating nips located 100 mm below the die with anacceleration of 2.4 mm/sec². The required tensile force is recorded as afunction of the take-up speed of the nip rolls. The maximum tensileforce attained during the test is defined as the melt strength. In thecase of polymer melt exhibiting draw resonance, the tensile force beforethe onset of draw resonance was taken as melt strength. The meltstrength is recorded in centiNewtons (“cN”).

Catalysts

The term “overnight”, if used, refers to a time of approximately 16-18hours, the term “room temperature”, refers to a temperature of 20-25°C., and the term “mixed alkanes” refers to a commercially obtainedmixture of C₆₋₉ aliphatic hydrocarbons available under the tradedesignation Isopar E®, from ExxonMobil Chemical Company. In the eventthe name of a compound herein does not conform to the structuralrepresentation thereof, the structural representation shall control. Thesynthesis of all metal complexes and the preparation of all screeningexperiments were carried out in a dry nitrogen atmosphere using dry boxtechniques. All solvents used were HPLC grade and were dried beforetheir use.

MMAO refers to modified methylalumoxane, a triisobutylaluminum modifiedmethylalumoxane available commercially from Akzo-Noble Corporation.

The preparation of catalyst (B1) is conducted as follows.)

a) Preparation of(1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)methylimine

3,5-Di-t-butylsalicylaldehyde (3.00 g) is added to 10 mL ofisopropylamine. The solution rapidly turns bright yellow. After stirringat ambient temperature for 3 hours, volatiles are removed under vacuumto yield a bright yellow, crystalline solid (97 percent yield).

b) Preparation of1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconium dibenzyl

A solution of (1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)imine (605mg, 2.2 mmol) in 5 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (500 mg, 1.1 mmol) in 50 mL toluene. The resulting darkyellow solution is stirred for 30 min. Solvent is removed under reducedpressure to yield the desired product as a reddish-brown solid.

The preparation of catalyst (B2) is conducted as follows.

a) Preparation of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine

2-Methylcyclohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol(90 mL), and di-t-butylsalicaldehyde (10.00 g, 42.67 mmol) is added. Thereaction mixture is stirred for three hours and then cooled to −25° C.for 12 hrs. The resulting yellow solid precipitate is collected byfiltration and washed with cold methanol (2×15 mL), and then dried underreduced pressure. The yield is 11.17 g of a yellow solid. ¹H NMR isconsistent with the desired product as a mixture of isomers.

b) Preparation ofbis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl

A solution of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine (7.63g, 23.2 mmol) in 200 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (5.28 g, 11.6 mmol) in 600 mL toluene. The resulting darkyellow solution is stirred for 1 hour at 25° C. The solution is dilutedfurther with 680 mL toluene to give a solution having a concentration of0.00783 M.

Cocatalyst 1 A mixture of methyldi(C₁₄₋₁₈ alkyl)ammonium salts oftetrakis(pentafluorophenyl)borate (here-in-after armeenium borate),prepared by reaction of a long chain trialkylamine (Armeen™ M2HT,available from Akzo-Nobel, Inc.), HCl and Li[B(C₆F₅)₄], substantially asdisclosed in U.S. Pat. No. 5,919,983, Ex. 2.

Cocatalyst 2 Mixed C₁₄₋₁₈ alkyldimethylammonium salt ofbis(tris(pentafluorophenyl)-alumane)-2-undecylimidazolide, preparedaccording to U.S. Pat. No. 6,395,671, Ex. 16.

Shuttling Agents The shuttling agents employed include diethylzinc (DEZ,SA1), di(1-butyl)zinc (SA2), di(n-hexyl)zinc (SA3), triethylaluminum(TEA, SA4), trioctylaluminum (SA5), triethylgallium (SA6),i-butylaluminum bis(dimethyl(t-butyl)siloxane) (SA7), i-butylaluminumbis(di(trimethylsilyl)amide) (SA8), n-octylaluminumdi(pyridine-2-methoxide) (SA9), bis(n-octadecyl)i-butylaluminum (SA 10),i-butylaluminum bis(di(n-pentyl)amide) (SA11), n-octylaluminumbis(2,6-di-t-butylphenoxide) (SA12), n-octylaluminumdi(ethyl(1-naphthyl)amide) (SA13), ethylaluminumbis(t-butyldimethylsiloxide) (SA14), ethylaluminumdi(bis(trimethylsilyl)amide) (SA15), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA16), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA17), n-octylaluminumbis(dimethyl(t-butyl)siloxide(SA18), ethylzinc (2,6-diphenylphenoxide)(SA19), and ethylzinc (t-butoxide) (SA20).

Examples 1-4, Comparative A-C General High Throughput ParallelPolymerization Conditions

Polymerizations are conducted using a high throughput, parallelpolymerization reactor (PPR) available from Symyx Technologies, Inc. andoperated substantially according to U.S. Pat. Nos. 6,248,540, 6,030,917,6,362,309, 6,306,658, and 6,316,663. Ethylene copolymerizations areconducted at 130° C. and 200 psi (1.4 MPa) with ethylene on demand using1.2 equivalents of cocatalyst 1 based on total catalyst used (1.1equivalents when MMAO is present). A series of polymerizations areconducted in a parallel pressure reactor (PPR) contained of 48individual reactor cells in a 6×8 array that are fitted with apre-weighed glass tube. The working volume in each reactor cell is 6000μL. Each cell is temperature and pressure controlled with stirringprovided by individual stirring paddles. The monomer gas and quench gasare plumbed directly into the PPR unit and controlled by automaticvalves. Liquid reagents are robotically added to each reactor cell bysyringes and the reservoir solvent is mixed alkanes. The order ofaddition is mixed alkanes solvent (4 ml), ethylene, 1-octene comonomer(1 ml), cocatalyst 1 or cocatalyst 1/MMAO mixture, shuttling agent, andcatalyst or catalyst mixture. When a mixture of cocatalyst 1 and MMAO ora mixture of two catalysts is used, the reagents are premixed in a smallvial immediately prior to addition to the reactor. When a reagent isomitted in an experiment, the above order of addition is otherwisemaintained. Polymerizations are conducted for approximately 1-2 minutes,until predetermined ethylene consumptions are reached. After quenchingwith CO, the reactors are cooled and the glass tubes are unloaded. Thetubes are transferred to a centrifuge/vacuum drying unit, and dried for12 hours at 60° C. The tubes containing dried polymer are weighed andthe difference between this weight and the tare weight gives the netyield of polymer. Results are contained in Table 1. In Table 1 andelsewhere in the application, comparative compounds are indicated by anasterisk (*).

Examples 1-4 demonstrate the synthesis of linear block copolymers by thepresent invention as evidenced by the formation of a very narrow MWD,essentially monomodal copolymer when DEZ is present and a bimodal, broadmolecular weight distribution product (a mixture of separately producedpolymers) in the absence of DEZ. Due to the fact that Catalyst (A1) isknown to incorporate more octene than Catalyst (B1), the differentblocks or segments of the resulting copolymers of the invention aredistinguishable based on branching or density.

TABLE 1 Cat. (A1) Cat (B1) Cocat MMAO shuttling Ex. (μmol) (μmol) (μmol)(μmol) agent (μmol) Yield (g) Mn Mw/Mn hexyls¹ A* 0.06 — 0.066 0.3 —0.1363 300502 3.32 — B* — 0.1 0.110 0.5 — 0.1581 36957 1.22 2.5 C* 0.060.1 0.176 0.8 — 0.2038 45526 5.30² 5.5 1 0.06 0.1 0.192 — DEZ (8.0) 0.1974 28715 1.19 4.8 2 0.06 0.1 0.192 — DEZ (80.0) 0.1468 2161 1.1214.4  3 0.06 0.1 0.192 — TEA (8.0)  0.208 22675 1.71 4.6 4 0.06 0.10.192 — TEA (80.0) 0.1879 3338 1.54 9.4 ¹C₆ or higher chain content per1000 carbons ²Bimodal molecular weight distribution

It may be seen the polymers produced according to the invention have arelatively narrow polydispersity (Mw/Mn) and larger block-copolymercontent (trimer, tetramer, or larger) than polymers prepared in theabsence of the shuttling agent.

Further characterizing data for the polymers of Table 1 are determinedby reference to the figures. More specifically DSC and ATREF resultsshow the following:

The DSC curve for the polymer of example 1 shows a 115.7° C. meltingpoint (Tm) with a heat of fusion of 158.1 J/g. The corresponding CRYSTAFcurve shows the tallest peak at 34.5° C. with a peak area of 52.9percent. The difference between the DSC Tm and the Tcrystaf is 81.2° C.

The DSC curve for the polymer of example 2 shows a peak with a 109.7° C.melting point (Tm) with a heat of fusion of 214.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 46.2° C. with a peak area of57.0 percent. The difference between the DSC Tm and the Tcrystaf is63.5° C.

The DSC curve for the polymer of example 3 shows a peak with a 120.7° C.melting point (Tm) with a heat of fusion of 160.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 66.1° C. with a peak area of71.8 percent. The difference between the DSC Tm and the Tcrystaf is54.6° C.

The DSC curve for the polymer of example 4 shows a peak with a 104.5° C.melting point (Tm) with a heat of fusion of 170.7 J/g. The correspondingCRYSTAF curve shows the tallest peak at 30° C. with a peak area of 18.2percent. The difference between the DSC Tm and the Tcrystaf is 74.5° C.

The DSC curve for comparative A shows a 90.0° C. melting point (Tm) witha heat of fusion of 86.7 J/g. The corresponding CRYSTAF curve shows thetallest peak at 48.5° C. with a peak area of 29.4 percent. Both of thesevalues are consistent with a resin that is low in density. Thedifference between the DSC Tm and the Tcrystaf is 41.8° C.

The DSC curve for comparative B shows a 129.8° C. melting point (Tm)with a heat of fusion of 237.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 82.4° C. with a peak area of 83.7 percent.Both of these values are consistent with a resin that is high indensity. The difference between the DSC Tm and the Tcrystaf is 47.4° C.

The DSC curve for comparative C shows a 125.3° C. melting point (Tm)with a heat of fusion of 143.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 81.8° C. with a peak area of 34.7 percent aswell as a lower crystalline peak at 52.4° C. The separation between thetwo peaks is consistent with the presence of a high crystalline and alow crystalline polymer. The difference between the DSC Tm and theTcrystaf is 43.5° C.

Examples 5-19, Comparatives D-F, Continuous Solution Polymerization,Catalyst A1/B2+DEZ

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil ChemicalCompany), ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, andhydrogen (where used) are supplied to a 3.8 L reactor equipped with ajacket for temperature control and an internal thermocouple. The solventfeed to the reactor is measured by a mass-flow controller. A variablespeed diaphragm pump controls the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst and cocatalyst 1 injection lines and thereactor agitator. These flows are measured by Micro-Motion mass flowmeters and controlled by control valves or by the manual adjustment ofneedle valves. The remaining solvent is combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters and are combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactoris run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer. Process details and results arecontained in Table 2. Selected polymer properties are provided in Table3.

TABLE 2 Process details for preparation of exemplary polymers Cat Cat A1Cat B2 DEZ DEZ Cocat Cocat Poly C₈H₁₆ Solv. H₂ T A1² Flow B2³ Flow ConcFlow Conc. Flow [C₂H₄]/ Rate⁵ Conv Solids Ex. kg/hr kg/hr sccm¹ ° C. ppmkg/hr ppm kg/hr % kg/hr ppm kg/hr [DEZ]⁴ kg/hr %⁶ % Eff.⁷ D* 1.63 12.729.90 120 142.2  0.14 — — 0.19 0.32  820 0.17 536 1.81 88.8 11.2 95.2 E*″  9.5 5.00 ″ — — 109 0.10 0.19 ″ 1743 0.40 485 1.47 89.9 11.3 126.8 F*″ 11.3 251.6 ″ 71.7 0.06 30.8 0.06 — — ″ 0.11 — 1.55 88.5 10.3 257.7 5 ″″ — ″ ″ 0.14 30.8 0.13 0.17 0.43 ″ 0.26 419 1.64 89.6 11.1 118.3 6 ″ ″4.92 ″ ″ 0.10 30.4 0.08 0.17 0.32 ″ 0.18 570 1.65 89.3 11.1 172.7 7 ″ ″21.70 ″ ″ 0.07 30.8 0.06 0.17 0.25 ″ 0.13 718 1.60 89.2 10.6 244.1 8 ″ ″36.90 ″ ″ 0.06 ″ ″ ″ 0.10 ″ 0.12 1778  1.62 90.0 10.8 261.1 9 ″ ″ 78.43″ ″ ″ ″ ″ ″ 0.04 ″ ″ 4596  1.63 90.2 10.8 267.9 10 ″ ″ 0.00 123 71.10.12 30.3 0.14 0.34 0.19 1743 0.08 415 1.67 90.31 11.1 131.1 11 ″ ″ ″120 71.1 0.16 ″ 0.17 0.80 0.15 1743 0.10 249 1.68 89.56 11.1 100.6 12 ″″ ″ 121 71.1 0.15 ″ 0.07 ″ 0.09 1743 0.07 396 1.70 90.02 11.3 137.0 13 ″″ ″ 122 71.1 0.12 ″ 0.06 ″ 0.05 1743 0.05 653 1.69 89.64 11.2 161.9 14 ″″ ″ 120 71.1 0.05 ″ 0.29 ″ 0.10 1743 0.10 395 1.41 89.42 9.3 114.1 152.45 ″ ″ ″ 71.1 0.14 ″ 0.17 ″ 0.14 1743 0.09 282 1.80 89.33 11.3 121.316 ″ ″ ″ 122 71.1 0.10 ″ 0.13 ″ 0.07 1743 0.07 485 1.78 90.11 11.2 159.717 ″ ″ ″ 121 71.1 0.10 ″ 0.14 ″ 0.08 1743 ″ 506 1.75 89.08 11.0 155.6 180.69 ″ ″ 121 71.1 ″ ″ 0.22 ″ 0.11 1743 0.10 331 1.25 89.93 8.8 90.2 190.32 ″ ″ 122 71.1 0.06 ″ ″ ″ 0.09 1743 0.08 367 1.16 90.74 8.4 106.0 *Comparative, not an example of the invention ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconiumdibenzyl ⁴molar ratio in reactor ⁵polymer production rate ⁶percentethylene conversion in reactor ⁷efficiency, kg polymer/g M where g M = gHf + g Zr

TABLE 3 Properties of exemplary polymers Heat of Tm − CRYSTAF Density MwMn Fusion T_(m) T_(c) T_(CRYSTAF) T_(CRYSTAF) Peak Area Ex. (g/cm³) I₂I₁₀ I₁₀/I₂ (g/mol) (g/mol) Mw/Mn (J/g) (° C.) (° C.) (° C.) (° C.)(percent) D* 0.8627 1.5 10.0 6.5 110,000 55,800 2.0 32 37 45 30 7 99 E*0.9378 7.0 39.0 5.6 65,000 33,300 2.0 183 124 113 79 45 95 F* 0.8895 0.912.5 13.4 137,300 9,980 13.8 90 125 111 78 47 20 5 0.8786 1.5 9.8 6.7104,600 53,200 2.0 55 120 101 48 72 60 6 0.8785 1.1 7.5 6.5 109600 533002.1 55 115 94 44 71 63 7 0.8825 1.0 7.2 7.1 118,500 53,100 2.2 69 121103 49 72 29 8 0.8828 0.9 6.8 7.7 129,000 40,100 3.2 68 124 106 80 43 139 0.8836 1.1 9.7 9.1 129600 28,700 4.5 74 125 109 81 44 16 10 0.8784 1.27.5 6.5 113,100 58,200 1.9 54 116 92 41 75 52 11 0.8818 9.1 59.2 6.566,200 36,500 1.8 63 114 93 40 74 25 12 0.8700 2.1 13.2 6.4 101,50055,100 1.8 40 113 80 30 83 91 13 0.8718 0.7 4.4 6.5 132,100 63,600 2.142 114 80 30 81 8 14 0.9116 2.6 15.6 6.0 81,900 43,600 1.9 123 121 10673 48 92 15 0.8719 6.0 41.6 6.9 79,900 40,100 2.0 33 114 91 32 82 10 160.8758 0.5 3.4 7.1 148,500 74,900 2.0 43 117 96 48 69 65 17 0.8757 1.711.3 6.8 107,500 54,000 2.0 43 116 96 43 73 57 18 0.9192 4.1 24.9 6.172,000 37,900 1.9 136 120 106 70 50 94 19 0.9344 3.4 20.3 6.0 76,80039,400 1.9 169 125 112 80 45 88

The resulting polymers are tested by DSC and ATREF as with previousexamples. Results are as follows:

The DSC curve for the polymer of example 5 shows a peak with a 119.6° C.melting point (Tm) with a heat of fusion of 60.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 47.6° C. with a peak area of59.5 percent. The delta between the DSC Tm and the Tcrystaf is 72.0° C.

The DSC curve for the polymer of example 6 shows a peak with a 115.2° C.melting point (Tm) with a heat of fusion of 60.4 J/g. The correspondingCRYSTAF curve shows the tallest peak at 44.2° C. with a peak area of62.7 percent. The delta between the DSC Tm and the Tcrystaf is 71.0° C.

The DSC curve for the polymer of example 7 shows a peak with a 121.3° C.melting point with a heat of fusion of 69.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 49.2° C. with a peak area of29.4 percent. The delta between the DSC Tm and the Tcrystaf is 72.1° C.

The DSC curve for the polymer of example 8 shows a peak with a 123.5° C.melting point (Tm) with a heat of fusion of 67.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.1° C. with a peak area of12.7 percent. The delta between the DSC Tm and the Tcrystaf is 43.4° C.

The DSC curve for the polymer of example 9 shows a peak with a 124.6° C.melting point (Tm) with a heat of fusion of 73.5 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.8° C. with a peak area of16.0 percent. The delta between the DSC Tm and the Tcrystaf is 43.8° C.

The DSC curve for the polymer of example 10 shows a peak with a 115.6°C. melting point (Tm) with a heat of fusion of 60.7 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 40.9° C. with apeak area of 52.4 percent. The delta between the DSC Tm and the Tcrystafis 74.7° C.

The DSC curve for the polymer of example 11 shows a peak with a 113.6°C. melting point (Tm) with a heat of fusion of 70.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 39.6° C. with apeak area of 25.2 percent. The delta between the DSC Tm and the Tcrystafis 74.1° C.

The DSC curve for the polymer of example 12 shows a peak with a 113.2°C. melting point (Tm) with a heat of fusion of 48.9 J/g. Thecorresponding CRYSTAF curve shows no peak equal to or above 30° C.(Tcrystaf for purposes of further calculation is therefore set at 30°C.). The delta between the DSC Tm and the Tcrystaf is 83.2° C.

The DSC curve for the polymer of example 13 shows a peak with a 114.4°C. melting point (Tm) with a heat of fusion of 49.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 33.8° C. with apeak area of 7.7 percent. The delta between the DSC Tm and the Tcrystafis 84.4° C.

The DSC for the polymer of example 14 shows a peak with a 120.8° C.melting point (Tm) with a heat of fusion of 127.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 72.9° C. with a peak area of92.2 percent. The delta between the DSC Tm and the Tcrystaf is 47.9° C.

The DSC curve for the polymer of example 15 shows a peak with a 114.3°C. melting point (Tm) with a heat of fusion of 36.2 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 32.3° C. with apeak area of 9.8 percent. The delta between the DSC Tm and the Tcrystafis 82.0° C.

The DSC curve for the polymer of example 16 shows a peak with a 116.6°C. melting point (Tm) with a heat of fusion of 44.9 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 48.0° C. with apeak area of 65.0 percent. The delta between the DSC Tm and the Tcrystafis 68.6° C.

The DSC curve for the polymer of example 17 shows a peak with a 116.0°C. melting point (Tm) with a heat of fusion of 47.0 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 43.1° C. with apeak area of 56.8 percent. The delta between the DSC Tm and the Tcrystafis 72.9° C.

The DSC curve for the polymer of example 18 shows a peak with a 120.5°C. melting point (Tm) with a heat of fusion of 141.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 70.0° C. with apeak area of 94.0 percent. The delta between the DSC Tm and the Tcrystafis 50.5° C.

The DSC curve for the polymer of example 19 shows a peak with a 124.8°C. melting point (Tm) with a heat of fusion of 174.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 79.9° C. with apeak area of 87.9 percent. The delta between the DSC Tm and the Tcrystafis 45.0° C.

The DSC curve for the polymer of comparative D shows a peak with a 37.3°C. melting point (Tm) with a heat of fusion of 31.6 J/g. Thecorresponding CRYSTAF curve shows no peak equal to and above 30° C. Bothof these values are consistent with a resin that is low in density. Thedelta between the DSC Tm and the Tcrystaf is 7.3° C.

The DSC curve for the polymer of comparative E shows a peak with a124.0° C. melting point (Tm) with a heat of fusion of 179.3 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 79.3° C. with apeak area of 94.6 percent. Both of these values are consistent with aresin that is high in density. The delta between the DSC Tm and theTcrystaf is 44.6° C.

The DSC curve for the polymer of comparative F shows a peak with a124.8° C. melting point (Tm) with a heat of fusion of 90.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 77.6° C. with apeak area of 19.5 percent. The separation between the two peaks isconsistent with the presence of both a high crystalline and a lowcrystalline polymer. The delta between the DSC Tm and the Tcrystaf is47.2° C.

Physical Property Testing

Polymer samples are evaluated for physical properties such as hightemperature resistance properties, as evidenced by TMA temperaturetesting, pellet blocking strength, high temperature recovery, hightemperature compression set and storage modulus ratio, G′(25°C.)/G′(100° C.). Several commercially available polymers are included inthe tests: Comparative G* is a substantially linear ethylene/1-octenecopolymer (AFFINITY®, available from The Dow Chemical Company),Comparative H* is an elastomeric, substantially linear ethylene/1-octenecopolymer (AFFINITY®EG8100, available from The Dow Chemical Company),Comparative I is a substantially linear ethylene/1-octene copolymer(AFFINITY®PL1840, available from The Dow Chemical Company), ComparativeJ is a hydrogenated styrene/butadiene/styrene triblock copolymer(KRATON™ G1652, available from KRATON Polymers), Comparative K is athermoplastic vulcanizate (TPV, a polyolefin blend containing dispersedtherein a crosslinked elastomer). Results are presented in Table 4.

TABLE 4 High Temperature Mechanical Properties Pellet 300% StrainCompres- TMA-1 mm Blocking Recovery sion Set penetration Strength G′(25°C.)/ (80° C.) (70° C.) Ex. (° C.) lb/ft² (kPa) G′(100° C.) (percent)(percent) D* 51 — 9 Failed — E* 130 — 18 — — F* 70 141 (6.8)  9 Failed100  5 104 0 (0) 6 81 49 6 110 — 5 — 52 7 113 — 4 84 43 8 111 — 4 Failed41 9 97 — 4 — 66 10 108 — 5 81 55 11 100 — 8 — 68 12 88 — 8 — 79 13 95 —6 84 71 14 125 — 7 — — 15 96 — 5 — 58 16 113 — 4 — 42 17 108 0 (0) 4 8247 18 125 — 10 — — 19 133 — 9 — — G* 75  463 (22.2) 89 Failed 100  H* 70 213 (10.2) 29 Failed 100  I* 111 — 11 — — J* 107 — 5 Failed 100  K* 152— 3 — 40

In Table 4, Comparative F (which is a physical blend of the two polymersresulting from simultaneous polymerizations using catalyst A 1 and B1)has a 1 mm penetration temperature of about 70° C., while Examples 5-9have a 1 mm penetration temperature of 100° C. or greater. Further,examples 10-19 all have a 1 mm penetration temperature of greater than85° C., with most having 1 mm TMA temperature of greater than 90° C. oreven greater than 100° C. This shows that the novel polymers have betterdimensional stability at higher temperatures compared to a physicalblend. Comparative J (a commercial SEBS) has a good 1 mm TMA temperatureof about 107° C., but it has very poor (high temperature 70° C.)compression set of about 100 percent and it also failed to recover(sample broke) during a high temperature (80° C.) 300 percent strainrecovery. Thus the exemplified polymers have a unique combination ofproperties unavailable even in some commercially available, highperformance thermoplastic elastomers.

Similarly, Table 4 shows a low (good) storage modulus ratio, G′(25°C.)/G′(100° C.), for the inventive polymers of 6 or less, whereas aphysical blend (Comparative E) has a storage modulus ratio of 9 and arandom ethylene/octene copolymer (Comparative G) of similar density hasa storage modulus ratio an order of magnitude greater (89). It isdesirable that the storage modulus ratio of a polymer be as close to 1as possible. Such polymers will be relatively unaffected by temperature,and fabricated articles made from such polymers can be usefully employedover a broad temperature range. This feature of low storage modulusratio and temperature independence is particularly useful in elastomerapplications such as in pressure sensitive adhesive formulations.

The data in Table 4 also demonstrate that the polymers of the inventionpossess improved pellet blocking strength. In particular, Example 5 hasa pellet blocking strength of 0 MPa, meaning it is free flowing underthe conditions tested, compared to Comparatives F and G which showconsiderable blocking. Blocking strength is important since bulkshipment of polymers having large blocking strengths can result inproduct clumping or sticking together upon storage or shipping,resulting in poor handling properties.

High temperature (70° C.) compression set for the inventive polymers isgenerally good, meaning generally less than about 80 percent, preferablyless than about 70 percent and especially less than about 60 percent. Incontrast, Comparatives F, G, H and J all have a 70° C. compression setof 100 percent (the maximum possible value, indicating no recovery).Good high temperature compression set (low numerical values) isespecially needed for applications such as gaskets, window profiles,o-rings, and the like.

TABLE 5 Ambient Temperature Mechanical Properties Tensile 100% 300%Retractive Compres- Stress Flex Elonga- Elonga- Abrasion: Notched StrainStrain Stress sion Relaxa- Modu- Tensile Tensile tion Tensile tionVolume Tear Recovery Recovery at 150% Set tion lus Modulus Strength atBreak¹ Strength at Break Loss Strength 21° C. 21° C. Strain 21° C. at50% Ex. (MPa) (MPa) (MPa)¹ (%) (MPa) (%) (mm³) (mJ) (percent) (percent)(kPa) (Percent) Strain² D* 12 5 — — 10 1074 — — 91 83 760 — — E* 895 589— 31 1029 — — — — — — — F* 57 46 — — 12 824 93 339 78 65 400 42 — 5 3024 14 951 16 1116 48 — 87 74 790 14 33 6 33 29 — — 14 938 — — — 75 86113 — 7 44 37 15 846 14 854 39 — 82 73 810 20 — 8 41 35 13 785 14 810 45461 82 74 760 22 — 9 43 38 — — 12 823 — — — — — 25 — 10 23 23 — — 14 902— — 86 75 860 12 — 11 30 26 — — 16 1090 — 976 89 66 510 14 30 12 20 1712 961 13 931 — 1247  91 75 700 17 — 13 16 14 — — 13 814 — 691 91 — — 21— 14 212 160 — — 29 857 — — — — — — — 15 18 14 12 1127  10 1573 — 2074 89 83 770 14 — 16 23 20 — — 12 968 — — 88 83 1040  13 — 17 20 18 — — 131252 — 1274  13 83 920  4 — 18 323 239 — — 30 808 — — — — — — — 19 706483 — — 36 871 — — — — — — — G* 15 15 — — 17 1000 — 746 86 53 110 27 50H* 16 15 — — 15 829 — 569 87 60 380 23 — I* 210 147 — — 29 697 — — — — —— — J* — — — — 32 609 — — 93 96 1900  25 — K* — — — — — — — — — — — 30 —¹Tested at 51 cm/minute ²measured at 38° C. for 12 hours

Table 5 shows results for mechanical properties for the new polymers aswell as for various comparison polymers at ambient temperatures. It maybe seen that the inventive polymers have very good abrasion resistancewhen tested according to ISO 4649, generally showing a volume loss ofless than about 90 mm³, preferably less than about 80 mm³, andespecially less than about 50 mm³. In this test, higher numbers indicatehigher volume loss and consequently lower abrasion resistance.

Tear strength as measured by tensile notched tear strength of theinventive polymers is generally 1000 mJ or higher, as shown in Table 5.Tear strength for the inventive polymers can be as high as 3000 mJ, oreven as high as 5000 mJ. Comparative polymers generally have tearstrengths no higher than 750 mJ.

Table 5 also shows that the polymers of the invention have betterretractive stress at 150 percent strain (demonstrated by higherretractive stress values) than some of the comparative samples.Comparative Examples F, G and H have retractive stress value at 150percent strain of 400 kPa or less, while the inventive polymers haveretractive stress values at 150 percent strain of 500 kPa (Ex. 11) to ashigh as about 1100 kPa (Ex. 17). Polymers having higher than 150 percentretractive stress values would be quite useful for elastic applications,such as elastic fibers and fabrics, especially nonwoven fabrics. Otherapplications include diaper, hygiene, and medical garment waistbandapplications, such as tabs and elastic bands.

Table 5 also shows that stress relaxation (at 50 percent strain) is alsoimproved (less) for the inventive polymers as compared to, for example,Comparative G. Lower stress relaxation means that the polymer retainsits force better in applications such as diapers and other garmentswhere retention of elastic properties over long time periods at bodytemperatures is desired.

Optical Testing

TABLE 6 Polymer Optical Properties Ex. Internal Haze (percent) Clarity(percent) 45° Gloss (percent) F* 84 22 49 G* 5 73 56 5 13 72 60 6 33 6953 7 28 57 59 8 20 65 62 9 61 38 49 10 15 73 67 11 13 69 67 12 8 75 7213 7 74 69 14 59 15 62 15 11 74 66 16 39 70 65 17 29 73 66 18 61 22 6019 74 11 52 G* 5 73 56 H* 12 76 59 I* 20 75 59

The optical properties reported in Table 6 are based on compressionmolded films substantially lacking in orientation. Optical properties ofthe polymers may be varied over wide ranges, due to variation incrystallite size, resulting from variation in the quantity of chainshuttling agent employed in the polymerization.

Extractions of Multi-Block Copolymers

Extraction studies of the polymers of examples 5, 7 and Comparative Eare conducted. In the experiments, the polymer sample is weighed into aglass fritted extraction thimble and fitted into a Kumagawa typeextractor. The extractor with sample is purged with nitrogen, and a 500mL round bottom flask is charged with 350 mL of diethyl ether. The flaskis then fitted to the extractor. The ether is heated while beingstirred. Time is noted when the ether begins to condense into thethimble, and the extraction is allowed to proceed under nitrogen for 24hours. At this time, heating is stopped and the solution is allowed tocool. Any ether remaining in the extractor is returned to the flask. Theether in the flask is evaporated under vacuum at ambient temperature,and the resulting solids are purged dry with nitrogen. Any residue istransferred to a weighed bottle using successive washes of hexane. Thecombined hexane washes are then evaporated with another nitrogen purge,and the residue dried under vacuum overnight at 40° C. Any remainingether in the extractor is purged dry with nitrogen.

A second clean round bottom flask charged with 350 mL of hexane is thenconnected to the extractor. The hexane is heated to reflux with stirringand maintained at reflux for 24 hours after hexane is first noticedcondensing into the thimble. Heating is then stopped and the flask isallowed to cool. Any hexane remaining in the extractor is transferredback to the flask. The hexane is removed by evaporation under vacuum atambient temperature, and any residue remaining in the flask istransferred to a weighed bottle using successive hexane washes. Thehexane in the flask is evaporated by a nitrogen purge, and the residueis vacuum dried overnight at 40° C.

The polymer sample remaining in the thimble after the extractions istransferred from the thimble to a weighed bottle and vacuum driedovernight at 40° C. Results are contained in Table 7.

TABLE 7 ether ether C₈ hexane hexane C₈ residue wt. soluble soluble molesoluble soluble mole C₈ mole Sample (g) (g) (percent) percent¹ (g)(percent) percent¹ percent¹ Comp. 1.097 0.063 5.69 12.2 0.245 22.35 13.66.5 F* Ex. 5 1.006 0.041 4.08 — 0.040 3.98 14.2 11.6 Ex. 7 1.092 0.0171.59 13.3 0.012 1.10 11.7 9.9 ¹Determined by ¹³C NMR

Additional Polymer Examples 19A-J, Continuous Solution Polymerization,Catalyst A1/B2+DEZ For Examples 19A-I

Continuous solution polymerizations are carried out in a computercontrolled well-mixed reactor. Purified mixed alkanes solvent (Isopar™ Eavailable from Exxon Mobil, Inc.), ethylene, 1-octene, and hydrogen(where used) are combined and fed to a 27 gallon reactor. The feeds tothe reactor are measured by mass-flow controllers. The temperature ofthe feed stream is controlled by use of a glycol cooled heat exchangerbefore entering the reactor. The catalyst component solutions aremetered using pumps and mass flow meters. The reactor is run liquid-fullat approximately 550 psig pressure. Upon exiting the reactor, water andadditive are injected in the polymer solution. The water hydrolyzes thecatalysts, and terminates the polymerization reactions. The post reactorsolution is then heated in preparation for a two-stage devolatization.The solvent and unreacted monomers are removed during the devolatizationprocess. The polymer melt is pumped to a die for underwater pelletcutting.

For Example 19J

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil ChemicalCompany), ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, andhydrogen (where used) are supplied to a 3.8 L reactor equipped with ajacket for temperature control and an internal thermocouple. The solventfeed to the reactor is measured by a mass-flow controller. A variablespeed diaphragm pump controls the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst and cocatalyst injection lines and thereactor agitator. These flows are measured by Micro-Motion mass flowmeters and controlled by control valves or by the manual adjustment ofneedle valves. The remaining solvent is combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters and are combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactoris run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer.

Process details and results are contained in Table 8. Selected polymerproperties are provided in Tables 9A-C.

In Table 9B, inventive examples 19F and 19G show low immediate set ofaround 65-70% strain after 500% elongation.

TABLE 8 Polymerization Conditions Cat A1² CatA1 Cat B2³ Cat B2 DEZ C₂H₄C₈H₁₆ Solv. H₂ T Conc. Flow Conc. Flow Conc Ex. lb/hr lb/hr lb/hr sccm¹° C. ppm lb/hr ppm lb/hr wt% 19A 55.29 32.03 323.03 101 120 600 0.25 2000.42 3.0 19B 53.95 28.96 325.3 577 120 600 0.25 200 0.55 3.0 19C 55.5330.97 324.37 550 120 600 0.216 200 0.609 3.0 19D 54.83 30.58 326.33 60120 600 0.22 200 0.63 3.0 19E 54.95 31.73 326.75 251 120 600 0.21 2000.61 3.0 19F 50.43 34.80 330.33 124 120 600 0.20 200 0.60 3.0 19G 50.2533.08 325.61 188 120 600 0.19 200 0.59 3.0 19H 50.15 34.87 318.17 58 120600 0.21 200 0.66 3.0 19I 55.02 34.02 323.59 53 120 600 0.44 200 0.743.0 19J 7.46 9.04 50.6 47 120 150 0.22 76.7 0.36 0.5 DEZ Cocat 1 Cocat 1Cocat 2 Cocat 2 Zn⁴ in Poly Poly- Flow Conc. Flow Conc. Flow polymerRate⁵ Conv⁶ mer Ex. lb/hr ppm lb/hr ppm lb/hr ppm lb/hr wt% wt% Eff.⁷19A 0.70 4500 0.65 525 0.33 248 83.94 88.0 17.28 297 19B 0.24 4500 0.63525 0.11  90 80.72 88.1 17.2 295 19C 0.69 4500 0.61 525 0.33 246 84.1388.9 17.16 293 19D 1.39 4500 0.66 525 0.66 491 82.56 88.1 17.07 280 19E1.04 4500 0.64 525 0.49 368 84.11 88.4 17.43 288 19F 0.74 4500 0.52 5250.35 257 85.31 87.5 17.09 319 19G 0.54 4500 0.51 525 0.16 194 83.72 87.517.34 333 19H 0.70 4500 0.52 525 0.70 259 83.21 88.0 17.46 312 19I 1.724500 0.70 525 1.65 600 86.63 88.0 17.6 275 19J 0.19 — — — — — — — — —¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconiumdimethyl ⁴ppm in final product calculated by mass balance ⁵polymerproduction rate ⁶weight percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Z

TABLE 9A Polymer Physical Properties Heat of Tm − CRYSTAF Density Mw MnFusion Tm Tc TCRYSTAF TCRYSTAF Peak Area Ex. (g/cc) I2 I10 I10/I2(g/mol) (g/mol) Mw/Mn (J/g) (° C.) (° C.) (° C.) (° C.) (wt%) 19A 0.87810.9 6.4 6.9 123700 61000 2.0 56 119 97 46 73 40 19B 0.8749 0.9 7.3 7.8133000 44300 3.0 52 122 100 30 92 76 19C 0.8753 5.6 38.5 6.9 81700 373002.2 46 122 100 30 92  8 19D 0.8770 4.7 31.5 6.7 80700 39700 2.0 52 11997 48 72  5 19E 0.8750 4.9 33.5 6.8 81800 41700 2.0 49 121 97 36 84 1219F 0.8652 1.1 7.5 6.8 124900 60700 2.1 27 119 88 30 89 89 19G 0.86490.9 6.4 7.1 135000 64800 2.1 26 120 92 30 90 90 19H 0.8654 1.0 7.0 7.1131600 66900 2.0 26 118 88 — — — 19I 0.8774 11.2 75.2 6.7 66400 337002.0 49 119 99 40 79 13 19J 0.8995 5.6 39.4 7.0 75500 29900 2.5 101 122106 — — —

TABLE 9B Polymer Physical Properties of Compression Molded FilmImmediate Immediate Immediate Recovery Recovery Recovery Density MeltIndex Set after Set after Set after after 100% after 300% after 500%Example (g/cm³) (g/10 min) 100% Strain (%) 300% Strain (%) 500% Strain(%) (%) (%) (%) 19A 0.878 0.9 15 63 131  85 79 74 19B 0.877 0.88 14 4997 86 84 81 19F 0.865 1 — — 70 — 87 86 19G 0.865 0.9 — — 66 — — 87 19H0.865 0.92 — 39 — — 87 —

TABLE 9C Average Block Index For exemplary polymers¹ Example Zn/C₂ ²Average BI Polymer F 0 0 Polymer 8 0.56 0.59 Polymer 19a 1.3 0.62Polymer 5 2.4 0.52 Polymer 19b 0.56 0.54 Polymer 19h 3.15 0.59¹Additional information regarding the calculation of the block indicesfor various polymers is disclosed in U.S. Patent Application Serial No.11/376,835, entitled “Ethylene/α-Olefin Block Interpolymers”, filed onMar. 15, 2006, in the name of Colin L. P. Shan. Lonnie Hazlitt, et. al.and assigned to Dow Global Technologies Inc., the disclose of which isincorporated by reference herein in its entirety. ²Zn/C₂ *1000 = (Znfeed flow*Zn concentration/1000000/Mw of Zn)/(Total Ethylene feedflow*(1-fractional ethylene conversion rate)/Mw of Ethylene)*1000.Please note that “Zn” in “Zn/C₂*1000” refers to the amount of zinc indiethyl zinc (“DEZ”) used in the polymerization process, and “C2” refersto the amount of ethylene used in the polymerization process.

Examples 20 and 21

The ethylene/α-olefin interpolymer of Examples 20 and 21 were made in asubstantially similar manner as Examples 19A-I above with thepolymerization conditions shown in Table 11 below. The polymersexhibited the properties shown in Table 10. Table 10 also shows anyadditives to the polymer.

TABLE 10 Properties and Additives of Examples 20-21 Example 20 Example21 Density (g/cc) 0.8800 0.8800 MI 1.3 1.3 Additives DI Water 100 DIWater 75 Irgafos 168 1000 Irgafos 168 1000 Irganox 1076 250 Irganox 1076250 Irganox 1010 200 Irganox 1010 200 Chimmasorb 2020 100 Chimmasorb2020 80

Irganox 1010 isTetrakismethylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)methane.Irganox 1076 isOctadecyl-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate. Irgafos 168is Tris(2,4-di-t-butylphenyl)phosphite. Chimasorb 2020 is1,6-Hexanediamine, N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-polymerwith 2,3,6-trichloro-1,3,5-triazine, reaction products with,N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine.

TABLE 11 Polymerization Conditions for Examples 20-21 Cat A1² Cat A1 CatB2³ Cat B2 DEZ C₂H₄ C₈H₁₆ Solv. H₂ T Conc. Flow Conc. Flow Conc Ex.lb/hr lb/hr lb/hr sccm¹ ° C. ppm lb/hr ppm lb/hr wt% 20 130.7 196.17712.68 1767 120 499.98 1.06 298.89 0.57 4.80942 3 21 132.1 199.22 708.231572 120 462.4 1.71 298.89 0.6 4.99984 3 7 DEZ Cocat 1 Cocat 1 Cocat 2Cocat 2 Zn⁴ in Poly Poly- Flow Conc. Flow Conc. Flow polymer Rate⁵ Conv⁶mer Ex. lb/hr ppm lb/hr ppm lb/hr ppm lb/hr wt% wt% Eff.⁷ 20 0.485634.36 1.24 402.45 0.478 131 177 89.25 16.94 252.04 21 0.47 5706.4 1.61289.14 1.36 129 183 89.23 17.52 188.11 * Comparative, not an example ofthe invention ¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconiumdibenzyl ⁴ppm Zinc in final product calculated by mass balance ⁵polymerproduction rate ⁶weight percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Z

Example 22 Improving the Ethylene/α-Olefin Multiblock InterpolymerProcess of Examples 1-21

Each of the above Examples 1-21 to produce ethylene/α-olefin multiblockinterpolymer may be repeated and a metal alkyl compound may be reactedwith an acid to produce a soluble metal ester; or an ionic surfactantmay be added to the reactor or reactor effluent after the reaction; or amixture comprising an antioxidant may be added to the product underconditions sufficient to avoid formation of significant amounts ofinsoluble metal or metal compounds derived from said metal alkylcompound; or the post-reactor heat exchanger may be purged with an inertgas under conditions to remove metal oxide from the post-reactor heatexchanger.

It is expected that the result will be a substantial reduction,hinderance, or even elimination of the majority of foulant of the heatexchanger. Also, it is expected that the resulting ethylene/α-olefinmultiblock interpolymer product will have an equal or improved color ascompared to the product of Examples 1-21.

Example 23 Adding Calcium Stearate

Ethylene/α-olefin multiblock interpolymer having a melt index of 15 anda density of 0.877 g/cc is produced in a similar manner to that Example19. Water is employed as a catalyst deactivator at a 1.5:1 molar ratiowith respect to the diethyl zinc chain shuttling agent. 500 ppm ofcalcium stearate (on a polymer basis) is added to the polymer streamjust prior to the post-reactor heat exchanger (PRH). The heat transferefficiency is measured by calculating a dimensionless U value based onthe flows and temperatures of the polymer stream and the heat transferfluid. On a continuous basis over a five day period the heat transferefficiency drop is less than about 1% per day whereas continuouslyproducing the same product in the absence of calcium stearate additioncauses the heat transfer efficiency to drop approximately 5% per day.The amount of fouling is dependent upon the amount of calcium stearateemployed as shown in the table below. The addition of calcium stearateat levels of approximately from about 2 to about 3 times as high as theamount of Zn in the polymer (on a mass basis) leads to post reactorheater fouling at a rate approximately 1/10th that of identical runsperformed without the addition of calcium stearate.

Effect of calcium stearate and zinc on post reactor heater fouling Zn inpolymer Calcium stearate Calcium Fouling (ppm) in polymer (ppm)stearate/Zn ratio (% per day) 240 0 0 5.2 240 200 0.83 2.6 240 300 1.251 240 500 2.1 0.4 180 500 2.8 0.5 240 750 3.1 0.25 130 500 3.9 0.25 2401250 5.2 0.5

Example 24 Reacting Octanoic Acid

Ethylene/α-olefin multiblock interpolymer is produced in a similarmanner as in Example 23 except that water was not employed as thecatalyst deactivator and calcium stearate is not added. Instead,octanoic acid is mixed with Isopar E at room temperature and then pumpedinto the approximately 17% polymer stream which is at approximately 140°C. and located prior to the PRH. The amount of octanoic acid employed is2 moles of acid for every mole of zinc in the process stream. Theefficiency of the PRH drops less than 0.1% per day over a six day periodas compared to an approximately 5% drop per day without the use ofoctanoic acid.

Example 25 Reacting Stearic Acid

Ethylene/α-olefin multiblock interpolymer is produced in a similarmanner as in Example 24 except that stearic acid is employed instead ofoctanoic acid. The efficiency of the PRH drops less than 0.1% per dayover a four day period as compared to an approximately 5% drop per daywithout the use of stearic acid.

Example 26 Adding a Mixture Comprising an Antioxidant

Ethylene/α-olefin multiblock interpolymer is produced in a similarmanner to that in examples 1-21 except that various additives are addedand the amount and temperature of water is varied during the catalystneutralization step as shown in the table below.

Irganox Irganox Irgastab 1076 ™ 1010 ™ FS 042 ™ Whiteness (ppm) (ppm)(ppm) index comments 250 200 0 46 antioxidant added before PRH 500 400 060 Double antioxidant added before PRH 0 0 0 33 1.5 eq water 0 0 0 270.5 eq waater 0 0 0 71 1.5 eq water at 75 C. 0 0 0 56 1.5 eq water with5% isopropyl alcohol 50 0 0 62 1.5 eq water 100 0 0 63 1.5 eq water 0 0100 66 1.5 eq water 0 0 200 59 1.5 eq water

The amount of zinc in each final product is approximately 240 ppm ascalculated by mass balance. It is determined that when necessary toincrease the water solubility, a small amount of an alcohol is useful tobreak surface tension. Similarly, increasing the water temperatureyields an increase in solubility. As the table above shows whitenessindex increases (gray color formation is mitigated) by addingantioxidants during the catalyst neutralization step, adding hot (>50C.) water temperature during the catalyst neutralization step, and/oradding an alcohol (e.g. isopropanol) during the catalyst neutralizationstep. That is if one consider the third row as the control a whitenessindex of 33 is obtained. When an antioxidant is added before the PRH asin rows 1, 2, 7 and 8 the whiteness index increases. When hot water isadded as in row 5 the whiteness index increases. Similarly, when oneadds alcohol with the water as in row 6 the whiteness index gets higher.Also if Irgastab FS 042™ stabilizer is added before the PRH, then thewhiteness index increases.

Example 27 Adding a Mixture Comprising Water and Stearic Acid

Ethylene/a-olefin multiblock interpolymer is produced in a similarmanner as in Example 23 except that a mixture of water and stearic acidare employed as the catalyst deactivator and calcium stearate is notadded. Instead, stearic acid is mixed with Isopar E at room temperatureand then pumped into the approximately 17% polymer stream which is atapproximately 140° C. along with the water and located prior to the PRH.The amount of octanoic acid employed is 1 mole of acid for every mole ofzinc in the process stream and the amount of water employed is 0.75moles of water for every mol of Zinc in the process stream. Theefficiency of the PRH can be expected to drop less than 0.1% per dayover a three day period as compared to an approximately 5% drop per daywithout the use of water and stearic acid.

Example 28 Adding a Mixture Comprising Water and Octanoic Acid

Ethylene/a-olefin multiblock interpolymer is produced in a similarmanner as in Example 23 except that a mixture of water and octanoic acidare employed as the catalyst deactivator and calcium stearate is notadded. Instead, octanoic acid is mixed with Isopar E at room temperatureand then pumped into the approximately 17% polymer stream which is atapproximately 140° C. along with the water and located prior to the PRH.The amount of octanoic acid employed is 1 mole of acid for every mole ofzinc in the process stream and the amount of water employed is 0.75moles of water for every mol of Zinc in the process stream. Theefficiency of the PRH can be expected to drop less than 0.1% per dayover a three day period as compared to an approximately 5% drop per daywithout the use of water and octanoic acid.

Example 29 Nitrogen Purge

Ethylene/α-olefin multiblock interpolymer is produced in a similarmanner to that in Examples 1-21. When polymer production is halted, asolvent is flowed through the post-reactor heat exchanger atapproximately 185 C. to dissolve any remaining polymer. Nitrogen is usedto pad all solvent out of the PRH. A filter bag is placed over oneoutlet of the PRH. Nitrogen is blown through the exchanger in a firstdirection toward the outlet. The filter bag is removed and a new oneinstalled at the opposite end of the PRH. Nitrogen is blown through theexchanger in the opposite direction. Prior to the nitrogen purge theheat transfer efficiency of the PRH is less than 65% of the value for acompletely clean exchanger while after the nitrogen purge the heattransfer efficiency of the PRH is greater than 90% of the value for aclean exchanger.

Example 30 Percolation Cleaning

A post reactor shell and tube heat exchanger heat exchanger comprising19 tubes is employed to produce a LLDPE (1 MI, 0.920 g/cc) in Isopar Eat 23% polymer concentration. The pressure is reduced at the inletpressure such that the ΔP (psi) (inlet pressure-outlet pressure) variesas shown below.

Run ΔP (psi) Run 1-A 39 Run 1-B 38 Run 2 48 Run 3 111 Run 4 188 Run 5197 Run 6 187 Run 7 210

Extremely high gel contamination levels are obtained beginning with run#3. This increases when maximum tube boiling is reached in run #4.During these runs a high degree of oxidation in both large and smallpellets may be observed. This oxidation turns the pellets and film gray.Microscopy of the gels and particles shows high concentrations ofseverely oxidized, crosslinked polymer typical of surfaces in thedevolatilization system. Such material requires longer periods of timeto form and is likely not produced by the boiling heat transfer. Rather,the degraded polymer may originate from dislodged long-term buildup inthe exchanger tube walls by the vigorous percolation effect of boiling.Gels decrease during run #4 and following. This suggests that theboiling action may clean the exchanger. Run #7, which is a repeat of run#4, also results in a high level of gel.

Although the foregoing invention has been described in some detail byway of illustration and example for purposes of clarity ofunderstanding, it will be readily apparent to those of ordinary skill inthe art in light of the teachings of this invention that certain changesand modifications may be made thereto without departing from the spiritor scope of the appended claims.

We claim:
 1. A composition comprising: (1) an ethylene/α-olefinmultiblock interpolymer which comprises: at least 50 mole percentethylene and is characterized by multiple blocks or segments of two ormore polymerized monomer units differing in chemical or physicalproperties; (2) a metal ester having the formula Zn₄O(CnH_(2n+1)CO₂)₆wherein n is from 5 to 20, and the composition is characterized by awhiteness index from 50 to
 100. 2. The composition of claim 1 whereinthe composition has a whiteness index of from 70 to
 100. 3. Acomposition comprising: (1) an ethylene/α-olefin multiblock interpolymerwhich comprises at least 50 mole percent ethylene and is characterizedby multiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties; (2) a metal ester havingthe formula Zn₄O(CnH_(2n+1)CO₂)₆ wherein n is from 5 to 20, and thecomposition is characterized by a whiteness index of about
 50. 4. Thecomposition of claim 3 wherein the composition comprises less than 100ppm metal oxide.
 5. The composition of claim 3 wherein the compositioncomprises less than 50 ppm zinc oxide.
 6. The composition of claim 3wherein the composition comprises less than 10 ppm zinc oxide.